SYNTHESIS, CHARACTERIZATION AND PROPERTIES OF … · 2014-01-17 · synthesis, characterization and properties of coordination- and low band gap polymers for potential catalytic and

SYNTHESIS, CHARACTERIZATION AND PROPERTIES OF COORDINATION-

AND LOW BAND GAP POLYMERS FOR POTENTIAL CATALYTIC AND

PHOTOVOLTAIC APPLICATIONS

BY

CHRISTOPHER M. MACNEILL

A Dissertation Submitted to the Graduate Faculty of

WAKE FOREST UNIVERSITY GRADUATE SCHOOL OF ARTS AND SCIENCES

in Partial Fulfillment of the Requirements

for the Degree of

DOCTOR OF PHILOSOPHY

Chemistry

May 2011

Winston-Salem, North Carolina

Approved by:

Ronald E. Noftle, Ph. D., Advisor

David L. Carroll, Ph. D., Chair

Christa L. Colyer, Ph.D.

Stephen B. King, Ph. D.

Abdessadek Lachgar, Ph. D.

ii

ACKNOWLEDGEMENTS

I would first like to acknowledge and extend my warmest regards and thanks to

my advisor, Dr. Ronald E. Noftle, who has supported and guided me through my research

over the past five years.

I would like to give a special thanks to Dr. Cynthia S. Day for her patience and

kindness while collecting my crystal structure data for the coordination polymers project.

I was not the best crystal grower, but with her skills and help, I didn’t have to be.

I also want to thank my committee members Dr. David L. Carroll, Dr.

Abdessadek Lachgar and Dr. S. Bruce King for excellent discussions in all phases of my

research, especially Dr. David L. Carroll and Dr. Robert C. Coffin for their mentoring

with the organic solar cell project. I’d like to thank my fellow group members at the

Wake Forest Center for Nanotechnology and Molecular Materials, especially Eric

Peterson, Wanyi Nie, Gregory Smith and Chanitpa Khantha.

I would like to acknowledge my current and former group members, Melissa

Donaldson, Amy Marts, Alex MacIntosh, Eric Tainsh and Kasha Patel. Dr. Jianjun Zhang,

and Sergio A. Gamboa for help with the coordination polymers project. I would also like

to thank my fellow graduate students in the department of chemistry for making the past

five years fun and enjoyable.

For my parents, Michael and Karen MacNeill, and my sisters, Kerri and Molly,

for supporting me always in whatever I endeavor. Without them, I wouldn’t be the person

I am today. The utmost thanks to my beautiful fiancée, Samantha Miller, who has stuck

with me through thick and thin. She is the most generous and kind-hearted person I’ve

had the chance to know and I love her with all my heart.

iii

TABLE OF CONTENTS

Page

Acknowledgements ii

Table of Contents iii

List of Figures ix

List of Schemes xiii

List of Equations xiii

List of Tables xiv

Abbreviations xv

Abstract xvii

Chapter

1. Introduction to 1

1.1. Coordination Polymers 1

1.1.1. Coordination Chemistry 1

1.1.2. Coordination Polymers 2

1.2. Tuning Pore Size and Functionality 3

1.3. Gas Adsorption Properties of Coordination Polymers 6

1.3.1. Carbon Dioxide Gas 6

1.3.2. Hydrogen Gas 7

1.4. Luminescent Properties of Coordination Polymers 8

1.4.1. Luminescence 8

1.4.2. Luminescence of Coordination Polymers 9

1.4.3. Luminescence of Lanthanide-based Coordination Polymers 9

iv

1.5. Catalytic Properties of Coordination Polymers 10

1.5.1. Zeolites vs. Coordination Polymers 10

1.5.2. Catalytic Sites in Coordination Polymers 11

1.5.3. Catalytic Reactions using Coordination Polymers 12

1.5.3.1. Cyanosilylation of Aldehydes 12

1.5.3.2. The Biginelli Reaction 14

1.5.3.3. Knoevenagel Condensation 15

1.6. Research Goal 17

2. Experimental 18

2.1. Materials 18

2.2. Methods 19

2.2.1. Analytical Methods 19

2.2.2. X-ray Diffraction Methods 19

2.3. Synthesis 20

2.3.1. Solvothermal Method 20

2.3.2. Reflux Method 22

2.3.3. Vapor Diffusion Method 23

2.3.4. Catalytic Experiments 25

2.3.4.1. Heterogeneous Catalysts 25

2.3.4.2. Homogeneous Catalysts 27

3. Synthesis, Crystal Structure and Properties of Coordination Polymers 1-4 28 3.1. Synthesis of Coordination Polymers 1-4 29

v

3.2. Single Crystal X-ray Diffraction 29 3.2.1. Crystal structure of La2(2,5-TDC)3(DMF)2H2O

. DMF (1) 29 3.2.2. Crystal structure of Gd2(2,5-TDC)3(DMF)2H2O (2) 32 3.2.3. Crystal structure of Eu4(C6H2O4S)6(H2O)2(DMF)3

(H2O/n-prOH) (3) 35 3.2.4. Crystal structure of Y(2,5-TDC)(DMF)2(NO3) (4) 37 3.3. Thermogravimetric Analysis 38 3.4. Infrared Spectroscopy 39 3.5. Solid State Photoluminescence 42 3.6. Catalytic Properties 43 3.7. Conclusion 46

4. Synthesis, Crystal Structure and Properties of Coordination Polymers 5-9 48 4.1. Synthesis of Coordination Polymers 5-9 49 4.2. Single Crystal X-ray Diffraction 50 4.2.1. Crystal Structure of Tb2(F4BDC)3(DEF)2EtOH2

. 2(DEF) (5) 50

4.2.2. Crystal Structure of Gd2(F4BDC)3(DEF)2EtOH2

. 2(DEF) (6), Eu2(F4BDC)3-(DEF)2EtOH2

. 2(DEF) (7), La2(F4BDC)3-(DEF)2EtOH2

. 2(DEF) (8) and Nd2(F4BDC)3-(DEF)2EtOH2

. 2(DEF) (9) 53

4.3. Thermogravimetric Analysis 53 4.4. Infrared Spectroscopy 54

vi

4.5. Solid State Photoluminescence 55 4.6. Catalytic Properties 57 4.7. Conclusion 59

5. Introduction to 61

5.1. The Environment 61

5.2. History of Photovoltaics 62

5.2.1. The Photoelectric Effect 62

5.2.2. Inorganic Photovoltaics 62

5.2.3. Organic Photovoltaics 64

5.3. Theory and Device Physics of Organic Solar Cells 65

5.3.1. Open Circuit Voltage 66

5.3.2. Short Circuit Current 67

5.3.3. Fill Factor 67

5.4. Device Architectures of Organic Solar Cells 69

5.5. Critical Parameters of Organic Solar Cells 70

5.6. Research Goal 73

6. Experimental 75

6.1 Materials 75

6.2. Methods 75

6.2.1. Analytical Methods 75

6.2.2. Electrochemical Methods 76

6.2.3. X-ray Diffraction Methods 76

6.2.4. Photovoltaic Methods 77

vii

6.3. Synthesis 78

7. Synthesis, Characterization and Photovoltaic Properties of P1-P3 87 7.1. Synthesis of Polymers P1-P3 88 7.2. Thermogravimetric Analysis of P1-P3 91 7.3. UV-Visible Spectroscopy of P1-P3 92 7.4. Electrochemistry of P1-P3 92 7.5. X-ray Powder Diffraction of P1-P3 94 7.6. Photovoltaic Properties of P1-P3 95 7.7. Conclusion 97

8. Synthesis, Characterization and Photovoltaic Properties of P4-P11 99 8.1. Synthesis of Polymers P4-P11 100 8.2. Thermogravimetric Analysis of P7-P11 103 8.3. UV-Visible Spectroscopy of P7-P11 104 8.4. Electrochemistry of P7-P11 105 8.5. X-ray Powder Diffraction of P7-P11 106 8.6. Photovoltaic Properties of P7-P11 108 8.7. Solvent Additive Processing of Polymer P11 110 8.8. Conclusion 113

9. Synthesis, Characterization and Photovoltaic Properties of P12-P14 115 9.1. Synthesis of Polymers P12-P14 116 9.2. Thermogravimetric Analysis of P12-P14 117 9.3. UV-Visible Spectroscopy of P12-P14 118

viii

9.4. Electrochemistry of P12-P14 119 9.5. X-ray Powder Diffraction of P12-P14 120 9.6. Photovoltaic Properties of P12-P13 122 9.7. Conclusion 124

Conclusions 126

Future Work 129

References 131

Appendix A 154

Appendix B 221

Publishing Permission and License 231

Scholastic Vitae 256

ix

List of Figures Page

Figure 1: Examples of coordination polymers with different dimensionalities. 2

Figure 2: The molecular building block (MBB) approach to coordination

polymers. Adapted from James.51 4 Figure 3: Organic linkers based on geometry for use in the synthesis of

coordination polymers. 5 Figure 4: Coordination environment around (a) La3+(1) and (b) La3+(2) ion. 30 Figure 5: (a) The La(1)-La(2) dimer formed by four bridging TDC2-

linkages. (b) A chain formed through linking of dimers from coordination polymer 1 shown down the a-axis. The La environment is shown as teal polyhedra, O (red), C (grey), S (yellow). 31

Figure 6: A perspective view of coordination polymer 1 along the a-axis

with solvent molecules omitted for clarity. 32 Figure 7: The coordination environments around (a) Gd3+(1) and

(b) Gd3+(2) ion. 33 Figure 8: (a) The Gd(1)-Gd(1) dimer formed by four bridging TDC2-

linkages. b) The Gd(2)-Gd(2) dimer formed by four bridging TDC2- linkages. c) A chain formed through the linking of dimers 1 and 2 down the a-axis for coordination polymer 2. The Gd environment is shown as blue polyhedra. 34

Figure 9: The coordination environments around the (a) Eu3+(1) ion and

(b) Eu3+(2) ion. 35 Figure 10: (a) The asymmetric unit of Eu(1) and Eu(2) (pink) linked by two

TDC2- (bridging) linkages along with eight TDC2- linkages (all monodentate), two DMF molecules and one H2O molecule (bridging) forming Eu4(2,5-TDC)6(DMF)3(H2O)2(H2O/n-prOH) (3). (b) A chain formed through the linking of dimers in (a) of coordination polymer 3 down the a-axis. Carboxylates are shown in red. 36

x

Figure 11: (a) A representation of the environment around the yttrium

ion in coordination polymer 4 along the crystallographic ab-plane. b) A view of coordination polymer 4 along the crystallographic a-axis. 37

Figure 12: The TGA curves of coordination polymers 1-4. 38 Figure 13: The infrared spectra of coordination polymer 1 at room temperature (RT) and after heating to 380oC (compound 1a). 40 Figure 14: X-ray powder diffraction spectra comparing the room temperature pattern to the patterns at 380oC and 900oC of coordination polymer 1. 41 Figure 15: (a) Excitation (inset) and emission spectra of coordination

polymer 3 excited at 390 nm. (b) Coordination polymer 3 under visible light (c) Coordination polymer 3 under UV light (long wavelength). 43

Figure 16: (a) A view of the contents of the asymmetric unit for

Tb2(F4BDC)3(DEF)2(EtOH)2 · 2(DEF) (5). Hydrogen atoms have been omitted for clarity. (b) A view of the formula unit of 5 with two identical terbium atoms. (c) A view of the formula unit of 5, where the contents of the polyhedra represent the terbium atoms. 51

Figure 17: (a) A view of the dimer of 5 connected to other dimers through

six F4BDC2- linkages. (b) A view of (a) forming an overall 2D sheet with solvent molecules and hydrogen atoms omitted for clarity. 52

Figure 18: (a) A view of the 2D sheet of coordination polymer 5 along the

b-axis. (b) The formation of a 3D layered topology from stacking of the infinite 2D sheets from (a). Lattice DEFs were omitted for clarity. 52

Figure 19: The TGA curves of coordination polymers 5-9. 54 Figure 20: The infrared spectra of coordination polymer 7 (as synthesized)

and coordination polymer 7a (after evacuation to remove solvent from the lattice.) 55

Figure 21: (a) A picture of Tb 5, Eu 7 and La 8 coordination polymers under

visible light. (b) A picture of Tb 5, Eu 7 and La 8 coordination polymers under UV light. (c) The solid state photoluminescence

xi

spectrum of Eu 7 excited at 392 nm. (d) The solid state photoluminescence spectrum of Tb 5 excited at 300 nm. 56

Figure 22: A schematic representation of the steps involved in generating

photocurrent in a donor-acceptor polymer solar cell device. 66 Figure 23: The J-V curve (black) of a BHJ solar cell device under

illumination. Characteristic open circuit voltage (Voc), short circuit current (Jsc) and FF (Area A/Area B), as well as the calculation of power conversion efficiency (PCE) are indicated on the figure. 68

Figure 24: A representation of (a) a bi-layer solar cell device, (b) a BHJ solar cell device and (c) a tandem solar cell device. 69 Figure 25: The TGA curve of P1 (black), P2 (blue) and P3 (red) under

argon at 5oC/min. 91 Figure 26: The UV-vis absorption spectra of P1 (black), P2 (blue) and

P3 (red) in DCB. 92 Figure 27: The cyclic voltammograms of P1 (black), P2 (blue) and P3 (red)

films drop-cast from chloroform solution. 93 Figure 28: (a) The integrated powder diffraction patterns for P1 (black),

P2 (blue) and P3 (red). Inset: 10 frames added together for P3. (b) A model of packing for P3. 95

Figure 29: Current-voltage characteristics of BHJ solar cells based

on P1 (black), P2 (blue) and P3 (red) with PC61BM. 96 Figure 30: External quantum efficiency spectra of BHJ solar cells based on

P1 (black), P2 (blue) and P3 (red) with PC61BM. 97 Figure 31: The UV-vis absorption spectra of P3 (red), P4 (black), P5

(green) and P6 (pink) in DCB. 102 Figure 32: The TGA curve of P7 (black), P8 (blue), P9 (orange), P10

(green) and P11 (red) under argon at 5oC/min. 103 Figure 33: The UV-vis absorption spectra of P7 (black), P8 (blue), P9

(orange), P10 (green) and P11 (red) in DCB. 104 Figure 34: The cyclic voltammograms of P7 (black), P8 (blue), P9 (orange),

P10 (green) and P11 (red) films drop-cast from chloroform solution. 105

xii

Figure 35: The powder diffraction patterns for P7 (black), P8 (blue) and

P9 (orange), P10 (green) and P11 (red). 107 Figure 36: Current-voltage characteristics of BHJ solar cells based on P7

(black), P8 (blue), P9 (orange), P10 (green) and P11 (red) with PC71BM. 109

Figure 37: External quantum efficiency spectra of BHJ solar cells based

on P7 (black), P8 (blue), P9 (orange), P10 (green) and P11 (red) with PC71BM. 110

Figure 38: Summary of chlorobenzene ratio on device performance. (a)

Summary of open circuit voltage and short circuit current density. (b) Summary of fill factor and power conversion efficiency. Points represent the average of at least eight devices with standard deviation. (c) The best current-voltage curves, and (d) the best external quantum efficiency curves for each condition. This figure is reproduced with permission from Wanyi Nie. 112

Figure 39: The TGA curve of P12 (blue), P13 (black) and P14 (red)

under argon at 10oC/min. 118 Figure 40: The UV-vis absorption spectra of P12 (blue), P13 (black)

and P14 (red) in chloroform solution. 119 Figure 41: The cyclic voltammograms of P12 (blue), P13 (black) and

P14 (red) films drop-cast from chloroform solution. 120 Figure 42: The powder diffraction patterns for P12 (blue), P13 (black) and

P14 (red) on loop. 121 Figure 43: Current-voltage characteristics of BHJ solar cells based on 1:1.5

(w:w) P12:PC61BM (blue) and 1:2.5 (w:w) P13:PC61BM (black) with 2 % DIO additive. 122

Figure 44: External quantum efficiency spectra of BHJ solar cells based on

1:1.5 (w:w) P12:PC61BM (blue) and 1:2.5 (w:w) P13:PC61BM with 2 % DIO additive (black). 123

xiii

List of Schemes Page Scheme 1: The cyanosilylation of aldehydes using a coordination polymer

(CP) as a heterogeneous catalyst. 12 Scheme 2: The Biginelli reaction using a CP as a heterogeneous catalyst. 14 Scheme 3: The Knoevenagel condensation reaction using a CP as a

heterogeneous catalyst. 16 Scheme 4: The Biginelli reaction using CP 1a as a heterogeneous catalyst. 44 Scheme 5: The proposed mechanism for the Biginelli reaction using an

activated coordination polymer as a heterogeneous catalyst. 46 Scheme 6: The synthesis of 4,8-dihydrobenzo[1,2-b;4,5-b’]dithiophene-

4,8-dione 28. 88 Scheme 7: The synthesis of the bis-stannylated monomers 34-37. 88 Scheme 8: The synthesis of polymers P1-P3. 89 Scheme 9: The synthesis of polymers P4-P6. 100 Scheme 10: The synthesis of polymers P7-P11. 101 Scheme 11: The synthesis of polymer P12. 116 Scheme 12. The synthesis of polymers P13-P14. 117

List of Equations

Equation 1. An equation relating the band gap (Eg) of a polymer to the open circuit voltage (Voc) by Baruch and co-workers.200 67

xiv

List of Tables Page Table 1: Catalytic syntheses of dihydropyrimidinones using CP 1a

and 2a under different reaction conditions.a 45 Table 2: Catalytic syntheses of dihydropyrimidinones using CP 7,

7a, 8 and 9 under different reaction conditions.a 58 Table 3: Table of results from electrochemical and UV-visible

spectroscopy measurements of polymers P1-P3. 93 Table 4: Photovoltaic characteristics of best devices prepared

from P1-P3 and PC61BM. 96 Table 5: Table of results from electrochemical and UV-visible


from P7-P11 and PC71BM. 110 Table 7: Table of results from electrochemical and UV-visible


from P12-P13 and PC61BM. 124 Table 9: A comparison of the photovoltaic characteristics of P13

at different (w:w) ratios PC61BM and using additive processing. The highest PCE for the devices can be seen in parenthesis. 124

xv

ABBREVIATIONS PSe 1,2,5-selenadiazolo[3,4-c]pyridine PT 1,2,5-thiadiazolo[3,4-c]pyridine BTC 1,3,5-benzenetricarboxylate DIO 1,8-diiodooctane BSe 2,1,3-benzoselenadiazole BT 2,1,3-benzothiadiazole F4BDC 2,3,5,6-tetrafluoro-1,4-terephthalic acid 2,5-TDC 2,5-thiophenedicarboxylate BDT Benzodithiophene CN Chloronapthalene CP Coordination Polymer CPDT Cylcopentadithiophene DCB Dichlorobenzene EQE External Quantum Efficiency FF Fill Factor HOMO Highest Occupied Molecular Orbital HIOM Hybrid Inorganic-Organic Material ITO Indium-Tin Oxide LUMO Lowest Unoccupied Molecular Orbital MOF Metal-Organic Framework DMF N,N-dimethylformamide Mn Number Average Molecular Weight

xvi

Voc Open Circuit Voltage OPV Organic Photovoltaic PCE Power Conversion Efficiency Jsc Short Circuit Current TGA Thermogravimetric Analysis TPD Thienopyrroledione

Mw Weight Average Molecular Weight

xvii

ABSTRACT Organic/Inorganic Polymeric Materials:

Four three dimensional-coordination polymers built of lanthanide ions and 2,5-

TDC2- linkers along with five isostructural two-dimensional lanthanide-based

coordination polymers with F4BDC linkers have been synthesized. The coordination

polymers were characterized by single-crystal and powder X-ray diffraction. For

Compounds 1-4, the Ln3+ metal ions are eight-coordinate, linked to other Ln3+ metal ions

by six 2,5-TDC2- units and varying amounts of coordinating solvent molecules. The metal

ions form a distorted sinusoidal chain which is bridged to other chains through 2,5-TDC2-

linkers to form a 3D framework. The solvent molecules occupy the rhombic channels of

the frameworks. For compounds 5-9, the Ln3+ metal ions are linked to an adjacent Ln3+

metal ions through the oxygen atoms of two bridging μ2-F4BDC2- ligands and two μ3-

F4BDC2- bridging ligands to form a Ln2O18 dimer. The Ln2O18 dimers are linked to each-

other through four F4BDC2- ligands to form 2D sheets. Compounds 1-9 were further

characterized using thermogravimetric analysis and infrared spectroscopy. Studies of the

photoluminescence properties of compounds 3, 5 and 7 as well as the catalytic activity of

compounds 1, 7, 8 and 9 in the Biginelli reaction, are presented.

Organic Polymeric Materials:

Through subtle manipulation of a solubilizing side chains on the backbone of 4,8-

dialkoxybenzo[1,2-b:4,5-b’]dithiophene (BDT)/2,1,3-benzothiadiazole (BT) copolymers,

the molecular weight and the solution processability of the polymers can be dramatically

improved. When 2-ethylhexyl side chains are attached to the 4- and 8-positions of the

xviii

BDT unit, a chloroform-soluble copolymer fraction with a weight-average molecular

weight (Mw) of 3.4 kg/mol is obtained (P2). By moving the ethyl branch from the 2- to

the 1- position on the hexyl chain, we obtain a chloroform soluble fraction with an Mw of

68.8 kg/mol (P3). As a result of this side chain alteration, the shape of the absorption

profile is dramatically altered, λmax is shifted from 575 to 637 nm, the hole mobility as

determined by thin film transistor (TFT) measurements is improved from 9 x 10-7 to 7 x

10-4 cm2/Vs, and the solar cell power conversion efficiency (PCE) of the bulk

heterojunction (BHJ) device is enhanced from 0.31 % to 2.91 %.

By further increasing the branch on the BDT backbone from a six carbon

branched chain to an eleven carbon branched chain (P7-P11), soluble high molecular

weight copolymers were achieved. Varying the co-monomer from 2,1,3-benzothiadiazole,

to other electron withdrawing monomers (P8-P10), allowed us to lower the band gap and

achieve decent efficiencies. High efficiency organic photovoltaic (OPV) devices

comprised of P11 and phenyl-C71-butyric acid methyl ester (PC71BM) were fabricated by

additive processing with 1-chloronapthalene (CN). When the active layer is cast from

pristine chlorobenzene, the average PCE is 1.41 %. Our best condition, using 2 %

chloronapthalene as a solvent additive in chlorobenzene, results in an average PCE of

5.65 %, with a champion efficiency of 6.05 %.

The donor monomer was varied from BDT to another donor monomer with a

lower band gap (cyclopentadithophene, CPDT) and compared to a known BDT-based

copolymer (P12) using the same thienopyrroledione acceptor monomer (P13). The

polymer showed excellent solubility at room temperature in chlorinated solvents. The

absorption onset for P1 is close to 740 nm as compared with ~685 nm for PBDTTPD,

xix

corresponding to an optical band gap of 1.67 eV, which is 0.15 eV lower than PBDTTPD.

The photovoltaic characteristics of the polymer were determined under AM 1.5g

illumination. The P13:PCBM BHJ device showed a high Voc (0.92 V) and Jsc (8.02

mA/cm2) as well as a good PCE (2.43 %), while the best device with 2% solvent additive

gave a PCE of 3.47 %.

1

CHAPTER 1: INTRODUCTION

1.1. Coordination Polymers

1.1.1. Coordination Chemistry

A coordination compound is a material that contains a central metal ion

surrounded by ligands that are coordinated to the metal center through coordination

bonds. Three features will determine how a coordination compound assembles: 1.) the

structure of the binding site; 2.) the spacer separating the binding sites and 3.) the

coordination environment around the metal center. 3 All three features have great bearing

on whether a certain ligand can coordinate to a metal ion. One can anticipate a certain

dimensionality to these motifs by understanding the properties of the metal and ligands.

These compounds are generally finite zero-dimensional (0D) materials. Many

coordination compounds can form other supramolecules such as cubes, cages,4-5 knots,6

catenanes,7 rotaxanes,8 clusters9 or helicates.10 They may have the ability to hydrogen

bond or π-π stack in three dimensions; however, coordination compounds usually contain

monodentate or bidentate ligands and these ligands form discrete 0D coordination

complexes. Coordination polymers, however, contain bi-, tri-, or tetradentate ligands,

which can coordinate to other metal centers and extend in all three dimensions to create

infinite extended structures (Figure 1). Many of the same rules outlined above for 0D

coordination compounds can be applied to multi-dimensional coordination polymers.

2

NN

Cu

NN

0D coordination compound

N N N NCu

Cl

ClH2O

H2OCl

ClCu

H2O

H2OCl

Cl

n

1D coordination polymer

N NCu

N

Cl

ClCu

N

Cl

Cl

N

N

N

N

N

N

N Cu

Cl

ClNCu

Cl

Cl

NCu

Cl

ClN Cu

Cl

Cl


N NCu

N

Cu

N

N

N

N

N

N

N

N CuNCu

NCu N Cu

N N

N N

N N

N N

N N

N N

N NCu

N

Cu

N

N

N

N

N

N

N

N CuNCu

NCu N Cu


1.1.2. Coordination Polymers

The term “coordination polymer” dates back to the 1960s when Balair compared

organic compounds to inorganic compounds that can be polymeric.11-12 Coordination

polymers are not polymeric in the sense that organic polymers are because they do not

have extended covalent bonds. Recently, the term “coordination polymers” (CP) has been

used interchangeably with the terms “metal-organic framework (MOF),” which was

coined by Yaghi in 1995,13 and hybrid inorganic-organic material (HIOM). A

coordination polymer is defined as “a metal coordination

Figure 1: Examples of coordination polymers with different dimensionalities.

3

compound in which a ligand bridges between metal centers, and in which each metal

center binds to more than one ligand to create an infinite array of metal centers.”14

Inorganic chemists tend to use the term “coordination polymer,” while solid state

chemists use “metal organic framework.”15 Metal-organic frameworks tend to exhibit a

three dimensional structure with permanent porosity, while coordination polymer is a

much broader term and encompasses all one-, two- and three-dimensional materials that

are polymeric. The metal acts as the node while the ligand acts as the spacer between

nodes to form infinite one-, two- or three-dimensional networks. 16 A significant amount

of research focuses on the crystal engineering aspect of coordination polymers in an

effort to form novel topologies. Coordination polymers have also become an increasingly

significant field of research due to their various applications in the areas of gas

adsorption,17-18 catalysis,19-21 magnetism,22 luminescence,23 and medicine.24-25

1.2 Tuning Pore Size and Functionality

The molecular building block approach26-29 (MBB) to functional materials is a

concept used to attempt to understand the dimensionality of the ensuing material before a

synthetic protocol is ever carried out. Knowing the coordination preferences of the metal,

along with the geometry of the spacer, one can predict the topology that will ensue from

the building blocks chosen (Figure 2). This ability to formulate novel topologies based on

coordination environment and ligand flexibility has been of interest to many research

groups. Use of a rigid linker as the backbone will allow for greater prediction of the

ensuing network geometry because of less orientational freedom of the ligand (Figure 3).

4

M M M MM

M MM

M

M

M

M

M

M

M

M M

M M

M

M

MM

M

M M

M

M

M M

M

metal coordination geometry organic linker geometry

1D chain

2D sheet

2D sheet 3D framework

Figure 2: The molecular building block (MBB) approach to coordination polymers.

Adapted from James.51

Guest solvent molecules will fill the voids left by the metal and ligands. These

frameworks should exhibit permanent porosity upon removal of guest solvent molecules

from the structure. The pore size of a CP is dictated by cautious choice of the organic

linker. The larger the organic spacer, the greater the potential pore size can be. If a linker

is large enough, and not rigid, the framework may interpenetrate, giving a smaller pore

sizes with potentially greater surface area. Transition metal-based CPs incorporating

Zn,30-31 Cd,32-33 Cu34-35 and Mn36-37 have been greatly explored; however, lanthanide-

based CPs are still in their infancy, mainly because of the lack of predictable topologies

due to their flexible coordination environments. Lanthanide ions are hard acids, and, thus,

5

N

N

CO2H

CO2HCO2H

CO2H

HO2C

HO2C

HO2C

CO2H

CO2H

CO2H

CO2H

HO2C

HO2C

N

N

N

N

N

N

CO2H

HO2C CO2H

organic linker geometry

HO2C CO2H

CO2H

S

S

CO2H

CO2H

CO2H

CO2H

CO2HHO2C

HO2C

HO2C

CO2H

CO2H

HO2C

O

O

O

O

organic ligands, which are hard bases, are required. Organic ligands, such as

dicarboxylates, are used for this purpose. The versatility of their coordination modes

makes them attractive linkers for bridging lanthanide centers. Recently most of the work

with lanthanide metal ions and O-donor ligands has been with rigid linkers such as 1,4-

benzenedicarboxylate, 1,2,4,5-benzenetetracarboxylate, 1,3,5-benzenetricarboxylate, and

biphenyl-3,3’,5,5’-tetracarboxylate.38-41 Coordination polymers based on 2,5-

thiophenedicarboxylic acid (2,5-TDC) are used in combination with another linker,

usually N-donor ligands such as pyridine, imidazole, bipyridine and 1,10-

phenanthroline.42-47 Only a few groups have engineered 2,5-TDC frameworks with

strictly 2,5-TDC as the O-donor48-50 Thiophene-based molecules have been known to

conduct charge extremely well. This is due to the lone pair of electrons on the sulfur atom,

which are easily delocalized around the ring.51

Figure 3: Organic linkers based on geometry for use in the synthesis of coordination

polymers

6

Other thiophene-based linkers such as 2,2’-bithiophene-5,5’-dicarboxylic acid52-53 and

thieno[3,2-b]thiophene-2,5-dicarboxylate,54-55 have been used as building blocks for the

synthesis of porous CPs.

1.3. Gas Adsorption Properties of Coordination Polymers

1.3.1. Carbon Dioxide Gas Adsorption

The increased amount of carbon dioxide (CO2) gas in the atmosphere, and its

impact on global warming has become a valid concern in our society. There are a few

ways to diminish the amount of CO2 entering the atmosphere, such as replacing fossil

fuels with nuclear power, using fuel cell technologies or trying to capture CO2 exhaust

from power plants before it is released into the atmosphere. Coordination polymers allow

us to address the latter. The ability to sequester and store CO2 will address the

environmental concerns raised by the emission of too much carbon dioxide. Currently,

fossil fuel plants are capturing CO2 by treating the gas with an amine solution. However,

this process is neither cost-, nor energy-efficient.56-57 Using these techniques, many

carbon-based materials58-60 and metal oxides61-62 have been tried, but these systems need

high reaction temperatures to adsorb CO2. Some coordination polymers offer a more

efficient way to capture CO2 at lower reaction temperatures and lower enthalpies of

adsorption. They also show good selectivity towards CO2 in gas mixtures with CH4, CO

and N2.63-64

Numerous frameworks such as Zeolitic Imidazolate Framework (ZIF-69), Hong

Kong University of Science and Technology (HKUST-1), Materials Institut Lavoisier

(MIL-101), Metal-Organic Framework (MOF-5) and MOF-177 have been studied for

7

their CO2 adsorption properties in the literature.65-70 ZIF-69, a framework built on zinc

metal ions and imidazolate ligands, showed uptakes of 69 cm3/g CO2 at 270 K and 1 bar

and has a BET surface area of 1070 cm2/g at 77 K.66 HKUST-1 is a framework made up

of Cu(II) ions with 1,3,5-benzenetricarboxylic acid as a linker to form a 3D framework.

BET calculations showed a surface area of 1570 cm2/g and a CO2 uptake of 239 cm3/g at

298 K and 50 bar.65-67 MIL-101 is a framework built on trimeric Cr (III) ions and 1,4-

benzenedicarboxylic acid.65 This framework has the largest CO2 uptake published to date

at 896 cm3/g at 298 K and 50 bar.

1.3.2. Hydrogen Gas Adsorption

Hydrogen storage through use of hydrogen-oxygen fuel cells, has become of

interest as a way of reducing our dependence on foreign oil and also for generation of

cleaner emissions. Materials such as hydrogen in its gas, liquid, or metal hydride form,

carbon-based materials, and zeolites have been investigated for their potential “on board”

hydrogen storage capabilities;71-76 however, use of these materials has encountered many

problems. Hydrogen gas and liquid hydrogen are not the safest choices and large amounts

of hydrogen would be lost during the filling and storage process. Metal hydrides have

slow uptake and release kinetics, which means high temperatures are needed to liberate

the hydrogen from the metal and a large amount of energy must be expended for uptake

of hydrogen by the metal after it has been liberated.77 Investigations of the hydrogen

storage capabilities of materials with high surface areas such as zeolites and carbon based

materials have been reported; however, the heat of adsorption is small and uptake can be

achieved only at extremely low temperatures.

8

It wasn’t until 2003 that CPs received a lot of interest for their hydrogen

adsorption capabilities due to their tunable pore sizes and high porosity. Many zeolites

have surface areas around 900 m2/g, while some CPs have achieved surface areas of

10000 m2/g.78 MOF-5 was the first metal organic framework to be used for these

investigations because it was cheap and had a large surface area.79 Since then, hundreds

of reports on the hydrogen adsorption of CPs have been published. Many of these papers

show that, the greater the surface area of the framework, the greater the gravimetric

uptake of hydrogen by weight at 77K.80

1.4 Luminescent Properties of Coordination Polymers

1.4.1 Luminescence

There are two types of luminescence: fluorescence and phosphorescence.

Fluorescence is defined as the emission of light, after absorption of a photon of light at a

different wavelength. The emitted light is usually at a longer wavelength (lower energy)

than the absorbed light. This phenomenon was observed by George Stokes in 1852.89 He

was working with a material, fluorite (CaF2), at the time, which was doped with

europium and emitted blue light. The term “Stokes shift” was coined later as the shift

between the absorption maximum and emission maximum for a given electronic

transition.90 A material that absorbs ultraviolet light emits it at a longer wavelength,

typically in the visible region. Phosphorescence involves the absorption of a photon,

similar to fluorescence; however, there is a delay in the emission of the photon due to a

spin-forbidden transition. These phosphorescent lifetimes can last from several seconds

to hours.

9

1.4.2. Luminescence of Coordination Polymers

Coordination polymers, as possible luminescent materials, have only been

considered since the early 2000s. Coordination polymers containing lanthanide ions are

mainly used as electroluminescent devices or sensors because of their photophysical

properties.81-86 Unlike most organic light-emitting devices, lanthanide coordination

polymers have sharp emission bands that range over the entire visible spectrum (Eu, Tb

and Tm)87 to the near IR region (Nd, Er, Yb).88 Coordination polymers are interesting

luminescent materials because they exist in a crystalline form and have predictable

topologies. Removal of solvent molecules from the framework allows for greater

luminescence intensity because the solvent molecules can quench emission. Permanent

porosity, combined with the rigidity of the framework, may also lead to increased

luminescence lifetimes and other features not inherent in traditional inorganic complexes.

Permanent porosity allows the framework to adsorb certain molecules into the pores with

close proximity to the metal centers, which may lead to a red shift in their spectra and/or

help to increase the luminescence intensity of the material. The numerous coordination

modes of the metal ions, along with a variety of organic linkers to choose from, make

coordination polymers useful materials for future luminescent applications.

1.4.3 Luminescence of Lanthanide-based Coordination Polymers

The luminescence of pure lanthanide elements is typically weak, due to certain

selection rules. In order to circumvent this, an organic molecule is used to act as an

antenna. Typically, organic molecules that have π-bonds, which can absorb the incident

light and transfer it to the lanthanide metal for re-emission, are used. There are a few

10

ways luminescence can be produced in a lanthanide CP, as outlined by Houk et al.91 1.)

Through the organic linker: as outlined above, organic molecules have π-bonds which

can absorb incident light. The luminescence can come from the linker and the energy can

be transferred to the metal ion and emitted as luminescence. 2.) Through the metal ion:

transition metals tend to quench luminescence, except for some d10 elements.92-94

Lanthanide ions have weak luminescence due to parity forbidden transitions; however, by

using the antenna effect95 to absorb light and transfer it to the lanthanide metal, these

restrictions can be partially circumvented. 3.) Through adsorbed materials: certain

materials can be adsorbed into the pores of the framework which can help contribute to

luminescence if in close proximity to the metal ion. 4.) Through π-π interactions: if the

organic linkers within the framework are close enough to have a π-π interaction, this can

contribute to luminescence because an excited complex is formed and ligand-to-ligand

charge transfer (LLCT) can occur.

Lanthanide frameworks, bound to carboxylate linkers such as 1,4-

benzenedicarboxylic acid and 2,2-bipyridine-4,4’-dicarboxylic acid, have been studied in

terms of their photophysical properties.96-98

1.5. Catalytic Properties of Coordination Polymers

1.5.1 Zeolites vs. Coordination Polymers

Coordination polymers have been studied for their heterogeneous catalytic

properties.99-102, 107-112 Coordination polymers have the ability to function as catalysts if

one can incorporate a functionalized ligand or an active metal site into the framework

structure. These catalytically active CPs are analogous to zeolites, which have been

11

studied and utilized extensively for their heterogeneous catalytic properties. Zeolites are

materials that incorporate SiO4 and AlO4 tetrahedral centers linked together through the

oxygen atoms to other Si or Al centers. These microporous materials have channel sizes

<10 Å. Their well defined pores have allowed zeolites to be utilized in the petroleum

industry for cracking of hydrocarbons. Their high thermal stability makes them useful

catalysts under forcing conditions, where a thermally stable material is needed. Many

different zeolites have been synthesized; however, due to the tetrahedral coordination

environment and the bond length of the oxygen spacer, it has been difficult to obtain

zeolites with varied pore sizes. The usefulness of zeolites as catalytic materials is limited

to small organic molecules. Unlike zeolites, CPs can be synthesized with linkers of

varying sizes, linking metals of different coordination environments, to give an array of

porous materials with diverse channel shapes and sizes. Due to their chemical variety,

CPs can be tailored to catalyze certain reactions under milder conditions compared to

zeolites. Their channel size can be modified using different organic linkers to catalyze

reactions for substrates which are too large for zeolitic pores.

1.5.2. Catalytic Sites in Coordination Polymers

Catalytic sites in CPs can be generated in several ways. First, evacuating the

framework of coordinated solvent molecules will leave open metal sites that can act as

Lewis acid catalytic sites. Second, a functionalized organic linker, that has an attached

catalytic site, can be incorporated. Last, a material can be incorporated in the channel

(catenation) of the CP, which can act as the catalytic center for the material. In the

literature, there has been some confusion as to whether a CP is acting as the catalyst or

12

H

O

CP+ Me3SiCN

H

OSiMe3CN

CH2Cl2

whether some homogeneous material dissolved in solution is catalyzing the reaction.

Control experiments can be run in which the catalyst is filtered off after a certain time

period, and the filtrate can be monitored to see if catalysis persists. Also, there is some

debate over whether catalysis is occurring in the channels of the CP or on the surface of

the CP. Experiments have been conducted in which the size of the substrate was

increased to a dimension greater than the size of the cavity. There should be no catalysis

observed for these molecules which can not fit in the cavities of the framework.

1.5.3. Catalytic Reactions using Coordination Polymers

1.5.3.1 Cyanosilylation of Aldehydes

Fujita and co-workers found that a cadmium-based CP, [Cd(L)(H2O)2](NO3) (L =

4,4’-bipyridine), showed the ability to catalyze the cyanosilylation of aldehydes (Scheme

1).99 In particular, benzaldehyde was converted to 2-(trimethylsiloxy)phenylacetonitrile

in 77% yield. The framework was made up of an octahedral Cd (II) metal center linked

by four 4,4’-bipyridine units in the equatorial positions to form a two-dimensional 4,4-

network. The axial positions on the Cd metal center were occupied by water molecules

which were removed from the layers under vacuum. To investigate whether the CP

Scheme 1: The cyanosilylation of aldehydes using a coordination polymer (CP) as a

heterogeneous catalyst.

13

was acting as the catalyst, it was filtered from the reaction mixture and the filtrate was

allowed to stand. No further conversion was seen, indicating the CP was acting as the

catalyst for the reaction. The CP showed some selectivity to substrate. This selectivity

was due to the limited cavity size of the material. The catalyst was more active towards

2-Tolualdehyde than 3-tolualdehyde, while there was no conversion shown for 9-

anthraldehyde. The catalytic sites also showed preference for ortho-dihalobenzenes as

opposed to the meta or para isomers. This supported the author’s conclusion that the

catalytic sites can be selective towards different substrates.

Similar cyanosilylation reactions have been carried out with other coordination

polymers.100 [Cu3(BTC)2(H2O)3] (BTC: 1,3,5-benzenetricarboxylate) is a 3D

coordination polymer built on copper paddlewheel building blocks linked by 1,3,5-

benzenetricarboxylate ligands. Water molecules occupied the axial positions and were

removed under vacuum to give the activated catalyst. The framework showed permanent

porosity, which was confirmed by surface area measurements. The copper center

coordinates to the aldehyde and promotes the reaction. The framework showed little

conversion to the cyanosilyl product at room temperature (<5%); however, when the

temperature was raised to 45oC, a 57% conversion to the product was observed.

Long and co-workers showed that a Mn(II)-based CP (Mn3[(Mn4Cl)3(BTT)8

(CH3OH)10]2 (H3BTT: 1,3,5-benzenetristetrazol-5-yl)) can efficiently catalyze the

cyanosilylation of aldehydes.101 The framework catalyzed the transformation of

benzaldehyde in 98% yield at RT after nine hours, which was an improvement over

previous frameworks studied.99-100

14

R1

O

H+

H2N NH2

O

+O

O

O R1

N

HN O

O

OH

+ H2O

R1 = aryl

CP

Toluene or MeOH

Some limitations were seen when using CPs as heterogeneous catalysts with

transition metal-based CPs. If an electron-donating solvent was used during the reaction,

it could compete with the aldehyde for coordination to the metal center and no product

was observed. Also, some of the CPs could not be heated above a certain temperature

(50oC) or decomposition of the framework resulted.

Lanthanide-based CPs have also been used as Lewis acid catalysts in the reaction

involving the cyanosilylation of aldehydes. The Gd framework, [Gd(L-H2)(L-H3)(H2O)4]

(L = 2,2’-diethoxy-1,1’-binaphthalene-6,6’-bisphosphonic acid), built on bisphosphonate

ligands, adopted a 2D lamellar structure, which exhibits permanent porosity and can

catalyze the cyanosilylation of aldehydes in moderate yields (55-61 %).102 Results

indicate that the framework swells to incorporate the substrate into its structure and

promote the catalysis.

1.5.3.2 The Biginelli Reaction

Another organic reaction that uses the Lewis acid sites on the metal ion for

catalysis is known as the Biginelli reaction. The Biginelli reaction involves the

cyclocondensation of an aldehyde, a dicarbonyl compound and urea in the presence of a

catalytic amount of a Lewis acid to give a substituted dihydropyrimidinone (Scheme 2).

Scheme 2: The Biginelli reaction using a CP as a heterogeneous catalyst.

15

Dihydropyrimidinones and their derivatives have long been known to have important

pharmacological properties as anti-virals103 as well as other related medicinal

applications.104-106 The Biginelli reaction has been used to assess the catalytic properties

of rare earth frameworks in several studies.107-109 Lii and co-workers108 explored

[Gd(H2O)(C2O4)0.5(HPO3)] · H2O as a potential heterogeneous catalyst in the Biginelli

reaction. The CP was mixed with benzaldehyde, ethyl acetoacetate and urea in methanol

at room temperature with stirring for 3 days. The framework showed 52% conversion to

5-ethoxycarbonyl-6-methyl-4-phenyl-3,4-dihydro-pyrimidin-2(1H)-one. This result is

similar to those of Bao and co-workers,107 who used [Gd(C9N3H2O(PO3H)2

(PO3))(H2O)]ClO4·3H2O as a catalyst and obtained 68% conversion to the Biginelli

product under similar conditions.

Lii and co-workers109 also explored a new material, (H4APPIP)[Yb3(C2O4)5.5

(H2PO4)2] ·5H2O, for use as a catalyst in the Biginelli reaction under similar conditions.

The yield was considerably lower (27%) due to the catalysis taking place on the surface

and not in the channels of the framework.

1.5.3.3 The Knoevenagel Condensation

There are many examples of CPs catalyzing organic reactions using the available

Lewis acid sites on the metal ion. A second approach is functionalizing the organic linker

and using the linker as the catalytic site, instead of the metal center. This can be useful

when the organic linkers are bulky and the substrate’s availability to the metal centers is

prohibited. The synthesis can occur in one of two ways. First, one can utilize a

functionalized organic linker and carry it through the framework synthesis from the

16

H

O

CP+ RCH2CN

benzeneH

RNC

beginning; conversely, one can synthesize the framework and then post-synthetically

modify the linker in a subsequent reaction.

Hasegawa and co-workers110 reported a 3D CP based on octahedral Cd metal

centers coordinated by amide functionalized 1,3,5-benzenetricarboxylic acid linkers

{[Cd(4-btapa)2 (NO3)2].6H2O

.2DMF} (4-btapa =1,3,5-benzenetricarboxylic acid tris[N-

(4-pyrid-yl)amide]). They showed that the amide sites on the linker, which were

protruding into the channels, can catalyze a weakly basic organic reaction known as the

Knoevenagal condensation (Scheme 3).

Scheme 3: The Knoevenagel condensation reaction using a CP as a heterogeneous

catalyst.

The CP contained three-dimensional pores that were 4.7 x 7.3 Å in size. Their

group showed that, if the size of the cyano substrate is changed from malononitrile (6.9 x

4.5 Å) to ethyl cyanoacetate (10.3 x 4.5 Å), and finally cyanoacetic acid tert-butyl ester

(10.3 x 5.8 Å), the catalytic activity decreased dramatically. This indicated that the

catalysis is occurring in the channels of the CP and not on the surface.

Gascon and co-workers111 synthesized an amino-functionalized CP based on 2-

aminoterephthalic acid and Zn metal ions (IRMOF-3), which was first reported by

Yaghi’s group.112 They showed that IRMOF-3 had catalytic activity in the Knoevenagel

condensation, with yields of 99% after 2 hours when ethyl cyanoacetate and

17

benzaldehyde were used as the substrates. The IRMOF-3 catalyst was stable under the

reaction conditions and could be reused without loss of catalytic activity.

Research Goal

The goal of this research is to synthesize and characterize a variety of lanthanide

based coordination polymers. The coordination polymers will be based on commercially

available organic linkers such as 2,5-thiophenedicarboxylic acid (2,5-TDC) and 2,3,5,6-

tetrafluoro-1,4-terephthalic acid (F4BDC), which vary in their acid/base properties. The

slightly basic 2,5-TDC molecules will potentially form a framework that is more basic

than a framework based on the less basic linker, F4BDC. The compounds will be

completely characterized by single crystal x-ray diffraction and x-ray powder diffraction

along with thermogravimetric analysis and infrared spectroscopy. The luminescence

properties of the CPs will be studied along with the catalytic properties of the CPs in

some common organic reactions. Addition of fluorine-based functional groups to the

organic linker may decrease the pore size of the CPs. With this reduction in pore size, a

size selective catalyst will ensue. The F4BDC linker will potentially give a framework

with greater Lewis acid catalytic activity due to the electron withdrawing fluorine atoms

pulling electron density away from the lanthanide, making it more electropositive. The

Lewis acid catalyzed reaction chosen for this study is the Biginelli reaction.

18

CHAPTER 2: EXPERIMENTAL

2.1. Materials

EuCl3 (anhyd), La(NO3)3·6H2O, Gd(NO3)3·6H2O, and Eu(NO3)3·6H2O were

purchased from Johnson Matthey (Savannah, GA). 2,5-Thiophenedicarboxylic acid, N,N-

dimethylformamide, Nd(NO3)3·5H2O, Tb(NO3)3·5H2O, triethylamine, n-formyl

piperidine, acetic anhydride, potassium hydroxide, sodium bicarbonate, benzaldehyde

and ethyl acetoacetate, acetonitrile, chloroform-d, DMSO-d6 and n-propanol were

purchased from Sigma-Aldrich Chemical Co (Milwaukee, WI). 2,3,5,6-Tetrafluoro-1,4-

benzenedicarboxylic acid and 2,3,4,5-tetrabromothiophene were obtained from Matrix

Scientific Co (Columbia, SC). Urea, hexanes, ethyl acetate, ethyl-2-mercaptoacetate, m-

xylene, n-butyllithium in hexanes (1.6M), anhydrous diethyl ether and N,N-

diethylformamide (DEF) were obtained from Acros Chemical Co (Pittsburgh, PA).

Ethanol was purchased from Aaper Alcohol and Chemical Co (Shelbyville, KY).

Bromine, CuCl2, Mn(OAc)2, potassium carbonate, iodine, chromium trioxide,

concentrated sulfuric acid, concentrated acetic acid, concentrated hydrochloric acid,

toluene and methanol were purchased from Fisher Chemical Co (Milwaukee, WI).

Acetone-d6 and acetonitrile-d3 were obtained from Cambridge Isotope Labs Inc (Andover,

MA). HPLC grade acetonitrile was distilled prior to use. All other solvents were used as

received without further purification.

19

2.2. Methods

2.2.1. Analytical Methods

1H and 13C-NMR spectra were recorded on Bruker Avance DPX-300 and DPX-

500 NMR sprectrometers. Thermogravimetric analysis (weight between 5 and 20 mg)

was performed under air (40 mL/min) at a rate of 5oC/min from 40-900oC using a Perkin-

Elmer Pyris 1 TGA system. Infrared spectra were recorded over the 450-4000 cm-1 region

using KBr pellets on a Mattson Infinity FT-IR spectrometer or on a Perkin Elmer

Spectrum 100 spectrophotometer with an ATR sampling accessory equipped with a

diamond anvil. Elemental analyses were carried out by Atlantic Microlabs, Inc (Norcross,

GA). GC-MS data were recorded on an Agilent 6850 Series GC system coupled to an

Agilent 5973 Mass Selective Detector run in electron impact mode. A 50-split method

was chosen to run on an Agilent column (13 x 0.25 mm x 0.25 μm) at a ramp rate of

13oC/min from 50oC to 280oC. Solid state photoluminescence spectra were recorded on

an Alphascan fluorimeter from Photon Technologies International. The light source was a

150-W Xenon arc lamp with a Hamamatsu R666S photomultiplier tube.

2.2.2. X-Ray Diffraction Methods

Crystals suitable for single crystal x-ray diffraction were microscopically

examined, selected from solution and held on a slide cooled with dry ice to minimize loss

of solvent. Three dimensional intensity data for all compounds were measured on a

Bruker SMART APEX CCD area detector system at 193 K using Mokα radiation (λ =

0.7107Å). Data was corrected for absorption effects using the SADABS program.113 All

20

structures were determined and refined using the Bruker SHELXTL software package

(Version 6.1).114

X-Ray powder diffraction data were collected at room temperature using a

BRUKER P4 general-purpose four-circle X-ray diffractometer modified with a

GADDS/Hi-Star detector at 40 kv and 30 mA for Cukα radiation (λ = 1.5406Å). GADDS

software suite was used to control the goniometer.115 The samples were mounted on tape

and three frames were measured at 2θ = 5.2o, 28o and 48o with exposure time of 360

seconds/frame. The powder patterns were each merged and analyzed using the EVA

program to produce a single powder diffraction pattern.116 The simulated powder patterns

were calculated using Mercury Software for Windows.

2.3. Synthesis

2.3.1 Solvothermal Method

Preparation of La2(2,5-TDC)3(DMF)2(H2O) .DMF (1).

La(NO3)3 · 6H2O (66.2 mg, 0.152 mmol) and 2,5-thiophenedicarboxylic acid

(20.0 mg, 0.116 mmol) were added to a Pyrex tube containing DMF (0.75 mL) and n-

propanol (1 mL). The tube was frozen in a liquid nitrogen bath, flame-sealed under

vacuum, and heated to 105oC for 24 hours. The mixture was allowed to cool to room

temperature slowly at a rate of 2oC/min. The mixture was decanted, vacuum filtered, and

washed with DMF and ether to yield a colorless crystalline product which was allowed to

dry in air. Yield (21.4 mg, 58 %, based on 2,5-TDC). FT-IR (KBr): 3463 (br), 3087 (w),

2932 (w), 1666 (s), 1565 (br), 1525 (s), 1382 (s), 1110 (m), 1036 (m), 816 (m), 776 (s),

21

672 (m), 465 (s). Anal. Calc’d for C24H22La2N2O15S3: C, 30.26; H, 2.32; N, 2.94; Found:

C, 30.45; H, 2.39 ; N, 3.28.

Preparation of Gd2(2,5-TDC)3(DMF)2H2O (2).

The procedure was similar to that used for 1 with Gd(NO3)3 ·6H2O (58.4 mg,

0.129 mmol) and 2,5-TDC (11.1 mg, 0.0640 mmol) yielding a colorless crystalline

product Yield (19.4 mg, 92 %, based on 2,5-TDC). FT-IR (KBr): 3430 (br), 3118 (w),

2935 (w), 1669 (s), 1577 (br), 1531 (s), 1385 (br), 1107 (w), 801 (w), 775 (s), 677 (m),

474 (m). Anal. Calc’d for C24H22Gd2N2O15S3: C, 29.14; H, 2.24; N, 2.83; Found: C,

28.87; H, 2.14; N, 3.01.

Preparation of Eu4(2,5-TDC)6(DMF)3(H2O)2(H2O/n-prOH) (3).

The procedure was similar to that used for 1 with EuCl3 (60.0 mg, 0232 mmol)

and 2,5-TDC (11.5 mg, 0.132 mmol) yielding a colorless crystalline product. Yield (34.6

mg, 81 %, based on 2,5-TDC). FT-IR (KBr): 3457 (br), 3094 (w), 2935 (w), 1669 (s),

1599 (br), 1526 (s), 1437 (s), 1372 (br), 1103 (w), 1036 (w), 819 (w), 776 (s), 682 (m),

471 (m). Anal Calc’d for C24H20Eu2N2O14S3: C, 26.27; H, 2.10; N, 2.91; Found: C, 26.38;

H, 2.19; N, 2.71;

Preparation of Y(2,5-TDC)(DMF)2NO3 (4)

The procedure was similar to that used for 1 with Y(NO3)3·6H2O (95.7 mg, 0.262

mmol) and 2,5-TDC (12.0 mg, 0.0697 mmol) yielding a crystalline product. Yield (19.4

mg, 59 %, based on 2,5-TDC). FT-IR (KBr): 3457 (br), 3099 (w), 2939 (w), 1679 (br),

1531 (st), 1398 (br), 1110 (m), 1033 (w), 800 (w), 777 (s), 680 (m), 474 (m). Anal Calc’d

for C12H16N3O9SY: C, 30.85; H, 3.45; N, 2.91; Found: C, 28.67; H, 2.68;

22

2.3.2 Reflux Method

Preparation of La2(2,5-TDC)3(DMF)2(H2O) .DMF (1).

To a 10 mL 2-neck round-bottom flask equipped with a reflux condenser and a

stopper was added La(NO3)3 · 6H2O (216.4 mg, 0.520 mmol), 2,5-TDC (46.0 mg, 0.268

mmol), DMF (3 mL), and n-propanol (4 mL). After the contents dissolved, the stir bar

was removed and glass beads were added. The solution was flushed with argon and set to

reflux under argon for 15 h at 125oC. A colorless microcrystalline product appeared and

was separated by decanting the solvent. The product was filtered and washed with DMF

and diethyl ether. Yield (70 mg, 76 %, based on 2,5-TDC). FT-IR (KBr): 3500 (br), 3097

(w), 2935 (w), 1670 (s), 1575 (br), 1525 (s), 1394 (s), 1105 (m), 1035 (m), 817 (m), 773

(s), 676 (m), 464 (s). La2(2,5-TDC)3(DMF)n (1a) was formed by heating at 5oC/min to

250oC and holding for 1 hour. The evacuated framework was brought back to RT at

5oC/min and stored over argon until use.

Preparation of Gd2(2,5-TDC)3(DMF)2H2O (2).

The procedure was similar to that used for 1 with Gd(NO3)3 · 6H2O (247.6 mg,

0.549 mmol) and 2,5-TDC (60.6 mg, 0.352 mmol) which gave a colorless

microcrystalline product. Yield (100.9 mg, 87 %, based on 2,5-TDC). FT-IR (KBr): 3438

(br), 3119 (w), 2940 (w), 1669 (s), 1577 (s), 1531 (s), 1385 (br), 1107 (w), 794 (w), 775

(s), 677 (m), 472 (m). Gd2(2,5-TDC)3(DMF)n (2a) was formed by heating at 5oC/min to

250oC and holding for 1 hour. The evacuated framework was brought back to RT at

5oC/min and stored over argon until use.

23

Preparation of Eu4(2,5-TDC)6(DMF)3(H2O)2(H2O/n-prOH) (3)

The procedure was similar to that used for 1 with EuCl3 (74.8 mg, 0.290 mmol)

and 2,5-TDC (22.4 mg, 0.130 mmol) yielding a colorless microcrystalline product. Yield

(35.4 mg, 84 %, based on 2,5-TDC). FT-IR (KBr): 3475 (br), 3097 (w), 2936 (w), 1671

(s), 1599 (br), 1541 (s), 1437 (s), 1386 (br), 1108 (w), 1039 (w), 818 (w), 782 (s), 678

(m), 474 (m).

Preparation of Y(2,5-TDC)(DMF)2NO3 (4).

The procedure was similar to that used for 1 with Y(NO3)3·5H2O (365.8 mg, 1.00

mmol) and 2,5-TDC (54.2 mg, 0.3148 mmol) yielding a white microcrystalline product.

Yield (72.9 mg, 49.5 %, based on 2,5-TDC). FT-IR (KBr): 3450 (br), 3113 (w), 2944 (w),

1674 (s), 1583 (br), 1529 (s), 1386 (s), 1109 (w), 774 (s), 681 (m), 475 (m).

2.3.3. Vapor Diffusion Method

Preparation of Tb2(F4BDC)3(DEF)2(EtOH)2 .2 DEF (5)

Tb(NO3)3·5H2O (54.2 mg, 0.125 mmol) and H2F4BDC acid (41.8 mg, 0.176

mmol) were added to a 10 mL vial containing N’N-diethylformamide (6 mL) and

ethanol (1 mL) and dissolved. The vial was covered with parafilm which was pierced

several times with a needle and set inside a beaker containing ethanol (5 mL) and

triethylamine (0.2 mL). The beaker was then covered with parafilm and the mixture of

ethanol and triethylamine vapor was allowed to diffuse into the solution for a period of

48 hr. A white crystalline product formed which was washed with DEF and acetone and

allowed to dry in air. Yield: (44.7 mg, 52 %, based on F4BDC). Anal. Calc’d for

Tb2(F4BDC)3(DEF)2(EtOH)2-1.5(DEF): C, 37.12; H, 3.46. Found: C, 37.06; H, 3.52. FT-

24

IR (KBr): 3450 (br), 2989 (w), 2950 (w), 1652 (s), 1614(s), 1481 (s), 1411 (br), 1268 (m),

1216(m), 1128 (m), 995 (s), 827 (w), 738 (s), 661 (m), 480 (m).

Preparation of Gd2(F4BDC)3(DEF)2(EtOH)2 .2 DEF (6)

A similar procedure to that used for 5 with Gd(NO3)3·6H2O (88.7 mg, 0.196

mmol) and F4BDC (35.4 mg, 0.149 mmol) gave a white crystalline product. Yield (47.2

mg, 61 %, based on F4BDC). Anal. Calc’d (%) for Gd2(F4BDC)3(DEF)2(EtOH)2: C,

34.61; H, 2.60. Found: C, 34.95; H, 2.61. FT-IR (KBr): 3448 (br), 2989 (w), 2952 (w),

1648 (s), 1614(s), 1481 (s), 1411 (br), 1268 (m), 1214(m), 1128 (m), 983 (s), 827 (w),

738 (s), 659 (m), 478 (m).

Preparation of Eu2(F4BDC)3(DEF)2(EtOH)2 .2 DEF (7)

A similar procedure to that used for 5 with Eu(NO3)3·5H2O (55.4 mg, 0.124


mg, 64 %, based on F4BDC). Anal. Calc’d for Eu2(F4BDC)3(DEF)2(EtOH)2-0.4(DEF): C,

35.67 ; H, 2.87. Found: C, 35.63; H, 2.61. FT-IR (KBr): 3459 (br), 2996 (w), 2958 (w),

1648 (s), 1614(s), 1473 (s), 1413 (br), 1270 (m), 1216(m), 1128 (m), 995 (s), 827 (w),

788 (m), 750 (m), 659 (m), 480 (m). Eu2(F4BDC)3(DEF)n (7a) was formed by heating at

5oC/min to 150oC and holding for 1 hour. The evacuated framework was brought back to

RT at 5oC/min and stored over argon until use.

Preparation of La2(F4BDC)3(DEF)2(EtOH)2 .2 DEF (8)

A similar procedure to that used for 5 with La(NO3)3·6H2O (64.0 mg, 0.148


mg, 49 %, based on F4BDC). Anal. Calc’d for La2(F4BDC)3(DEF)2(EtOH)2-0.5(DEF): C,


25

1648 (s), 1614(s), 1475 (s), 1405 (br), 1268 (m), 1214(m), 1128 (m), 995 (s), 827 (w),

748 (s), 655 (m), 474 (m).

Preparation of Nd2(F4BDC)3(DEF)2(EtOH)2 .2 DEF (9)

A similar procedure to that used for 5 with Nd(NO3)3·6H2O (78.4 mg, 0.179


mg, 45 %, based on F4BDC). Anal. Calc’d for Nd2(F4BDC)3(DEF)2(EtOH)2-1.5(DEF): C,


1654 (s), 1616 (s), 1475 (s), 1409 (br), 1268 (m), 1214 (m), 1128 (m), 995 (s), 827 (w),

748 (s), 657 (m), 476 (m).

2.3.4. Catalytic Experiments

2.3.4.1. Heterogeneous Catalysis

Preparation of 5-(Ethoxycarbonyl)-6-methyl-4-phenyl-3,4-dihydropyrimidin-2(1H)-

one (10a)

Benzaldehyde (30 μL, 0.29 mmol), ethyl acetoacetate (35 μL, 0.28 mmol), urea

(30.0 mg, 0.49 mmol), 7a (21.8 mg, 0.014 mmol) and toluene (0.2 mL) were added to a

10 mL round-bottom flask equipped with a reflux condenser. The mixture was heated to

80oC for 1.5 hours, then cooled to RT and diluted with ethyl acetate. The catalyst was

filtered off and the ethyl acetate solution was washed with water (2 ×15 mL). The organic

phase was dried over MgSO4, filtered, and evaporated to give the crude product. The

product was purified by trituration in an ethyl acetate/petroleum ether solution to give

10a. Yield (40.5 mg, 50 %). FT-IR (KBr): 3230, 3101, 2974, 2918, 1713, 1697, 1642,

1465, 1418, 1341, 1313, 1291, 1218, 1085, 950, 771. 1H-NMR (DMSO), δ (ppm): 9.17 (s,

26

1H, NH); 7.71 (s, 1H, NH); 7.28 (m, 5H, Ar-H); 5.14 (d, 1H, CH); 3.98 (q, 2H, OCH2);

2.25 (s, 3H, CH3); 1.10 (t, 3H, OCH2). GC-MS (m/e, %): 260 [parent M+] (19); 231 (75);

214 (13); 183 (100); 155 (40); 137 (25); 110 (8); 77 (11); 40 (16).

Room temperature reactions followed the same procedure but, instead of heating,

the solution was stirred for three days at ambient temperature in toluene or MeOH (see

Table 3).

Preparation of 5-(Ethoxycarbonyl)-6-methyl-4-(3-thienyl)-3,4-dihydropyrimidin-

2(1H)-one (10b)

The procedure was similar to that used for 10a with 3-thiophenecarboxaldehyde

(60 μL, 0.29 mmol) in toluene (1 mL). The product was recrystallized from ethanol to

give 10b.Yield (29.6 mg, 13 %). FT-IR (KBr): 3220, 3096, 2968, 1720, 1697, 1645, 1457,

1419, 1369, 1319, 1291, 1228, 1086, 950, 763. 1H-NMR (DMSO), δ (ppm): 9.18 (s, 1H,

NH); 7.74 (s, 1H, NH); 7.45 (m, 1H, Ar-H); 7.15 (s, 1H, Ar-H); 6.98 (d, 1H, Ar-H); 5.21

(d, 1H, CH); 4.05 (q, 2H, OCH2); 2.22 (s, 3H, CH3); 1.15 (t, 3H, OCH2). GC-MS

(m/e, %): 266 [parent M+] (86); 237 (80); 219 (20); 193 (100); 183 (49); 155 (32); 137

(31); 110 (25); 40 (36).

Preparation of 5-(Ethoxycarbonyl)-6-methyl-4-(1-napthyl)-3,4-dihydropyrimidin-

2(1H)-one (10c)

The procedure was similar to that used for 10a with 1-napthylenecarboxaldehyde

(76 μL, 0.29 mmol) in toluene (1 mL) gave compound 10c after recrystallization from

ethanol. Yield (17.5 mg, 12 %). FT-IR (KBr): 3232, 3099, 2975, 2920, 1696, 1644, 1512,

1430, 1376, 1318, 1279, 1267, 1219, 1086, 1025, 949, 766. 1H-NMR (DMSO-d6): δ =

9.24 (s, 1H, NH); 8.30 (d, 1H, Ar-H); 7.95 (d, 1H, Ar-H); 7.85 (d, 1H, Ar-H); 7.73 (s, 1H,

27

NH); 7.55 (m, 4H, Ar-H); 6.05 (s, 1H, CH); 3.80 (q, 2H, OCH2); 2.36 (s, 3H, CH3); 0.81

(t, 3H, OCH2).

2.3.4.2. Homogeneous Catalysis

Preparation of 5-(Ethoxycarbonyl)-6-methyl-4-phenyl-3,4-dihydropyrimidin-2(1H)-

one (10a)

Benzaldehyde (50 μL, 0.49 mmol), ethyl acetoacetate (62 μL, 0.49 mmol), urea

(49.1 mg, 0.81 mmol), 7a (33.3 mg, 0.022 mmol) and water (0.5 mL) were added to a 10

mL round- bottom flask. The solution was stirred at ambient temperature for 3 days after

which the reaction mixture was diluted with ethyl acetate (10 mL) and washed with water

(2 × 15 mL). The organic phase was dried over MgSO4, filtered, and evaporated to give

the crude product. The product was purified by filtration of an ethyl acetate/petroleum

ether solution to give pure 10a. Characterization was by methods similar to that above.

28

CHAPTER 3

SYNTHESIS, CRYSTAL STRUCTURE AND PROPERTIES

OF COORDINATION POLYMERS 1-4

Christopher M. MacNeill, Cynthia S. Day, Sergio A. Gamboa, Abdessadek Lachgar and

Ronald E. Noftle

A section of this chapter was excerpted from a published manuscript in the Journal of

Chemical Crystallography, 2010, volume 40, pages 222-230, and is reprinted with

permission from the journal. All of the research presented was conducted by Christopher

M. MacNeill with help from Sergio A. Gamboa. Crystal Structure Data was compiled by

Cynthia S. Day. The manuscript was prepared by Christopher M. MacNeill and edited by

Abdessadek Lachgar and Ronald E. Noftle.

29

3.1 Synthesis of Coordination Polymers 1-4

A solvothermal method was employed in the synthesis of coordination polymers

1-4. Stoichiometric ratios of 4:1 and 2:1 lanthanide metal to 2,5-TDC were employed for

1-4 and in each case the same overall three-dimensional coordination polymer resulted.

Because of this, the use of 2:1 ratios of lanthanide metal to organic linker was chosen to

conserve linker.

In the course of our work, we discovered that the coordination polymers 1-4 could

also be prepared in bulk using a benchtop reflux method. In the case of the reflux method,

product was visible after 15 hr at 125oC. Slow cooling in this case was defined as

dropping the temperature by 20oC over ten minutes. Prepared in this manner, the product

was microcrystalline but, nevertheless, it retained the basic framework structure as shown

by comparison of the powder diffraction spectra with those for the products prepared

solvothermally (Appendix B4-B6).

In the case of both methods, the pH of the system was not adjusted. DMF was the

preferred solvent owing to the solubility of 2,5-TDC. N-Propanol was also chosen as

solvent due to enhanced crystal growth compared to that in DMF/H2O mixtures

3.2. Single Crystal X-Ray Diffraction

3.2.1. Crystal structure of La2(2,5-TDC)3(DMF)2H2O · DMF (1)

Compound 1 crystallizes in the orthorhombic space group Pna21 (no. 33). The

coordination polymer is built on lanthanum ions linked by TDC2- ligands. The

asymmetric unit contains two crystallographically different lanthanum ions (La(1) and

La(2)), three TDC2- ligands, two DMF molecules, one water molecule and one lattice

30

DMF molecule. The La(1) ion is eight-coordinated by six monodentate oxygen atoms

(O(12), O(21), O(13), O(31) and O(23)) from five different TDC2- ligands, one bidentate

(O(33) and O(34)) TDC2- ligand and an oxygen atom from a DMF molecule (Figure 4a).

(a) (b) Figure 4: Coordination environment around (a) La3+(1) and (b) La3+(2) ion.

The La-O bond lengths range from 2.392(7) Å and 2.562(9) Å, which is comparable to

other La-O bond distances.117-118 The larger bond length (2.869(6) Å) for O(34) is

attributed to the μ3-TDC2- coordination mode that is seen with other lanthanum-based

coordination polymers.119 The coordination environment around La(2) consists of six

oxygen atoms from six TDC2- (O(11), O(14), O(22), O(24),O(32), and O(34)) with bond

lengths between 2.430(6) Å and 2.569(6) Å, one oxygen (O(2)) from DMF with La(2)-

O(2) = 2.587(7) Å) and one oxygen (O(4)) from the water molecule with La(2)-O(4) =

2.674(5) Å) (Figure 4b). The two lanthanum ions are linked by the carboxylate oxygen

atoms from four TDC2- ligands to form dimers with La(1)-La(2) distances of 4.2678(9) Å

(Figure 5a).

31

(a) (b) Figure 5: (a) The La(1)-La(2) dimer formed by four bridging TDC2--

linkages. (b) A chain

formed through linking of dimers from coordination polymer 1 shown down the a-axis.

The La environment is shown as teal polyhedra, O (red), C (grey), S (yellow).

The dimers are connected by two TDC2- ligands through (O(21), O(22), O(31)

and O(32)) to form distorted chains along the crystallographic a-axis (Figure 5b). Two

planes were drawn through La(1) and La(2) atoms along the a-axis and the angle between

those planes is 124.61o. The torsion angle for (La(1)-La(2)-La(1)-La(2)) is 0.838o, which

means the lanthanum ions in the chain do not lie directly on-top of each other if viewed

down the a-axis. The La-O bond lengths for this linkage range from 2.400(6) Å for

La(1)-O(21) to 2.540(7) Å for La(2)-O(22).

Each chain is linked to four adjacent chains via the oxygen atoms from four

TDC2- ligands to form a neutral three-dimensional 4,4- network with large diamond

shaped channels (6.7 X 6.7 Å) along the a-axis, where the DMF and water molecules

are located (Figure 6).

32

Figure 6: A perspective view of coordination polymer 1 along the a-axis with solvent

molecules omitted for clarity.

3.2.2. Crystal structure of Gd2(2,5-TDC)3(DMF)2H2O (2)

Compound (2) crystallizes in a monoclinic P21/n space group and forms an

overall neutral 3D coordination network that is very similar to that of compound 1. The

asymmetric unit contains two gadolinium ions, three TDC2- ligands, two DMF molecules

and one water molecule. The gadolinium ion Gd(1) is eight-coordinate and attached to

five TDC2- oxygen atoms (O(3a), O(4a), O(4b) O(2a), O(1)), one bidentate TDC2- (O(3b),

O(4b)), and one oxygen atom (O(5)) from the terminal DMF molecule (Figure 7a). The

Gd(1)-O distances of the TDC2- ligand range from 2.3061 Å to 2.4399 Å, which is in

agreement with those in the literature.120-121 The bond distances for the bidentate TDC2-

(O(4b)-Gd(1)-O(3b)) are 2.5879(59) Å and 2.4399(57) Å, respectively.

33

(a) (b)

Figure 7: The coordination environments around the (a) Gd3+(1) and (b) Gd3+(2) ion.

The corresponding gadolinium ion Gd(2) is eight-coordinate with six TDC2- bridging

oxygen atoms (O(1a), O(1b), O(2), O(4), O(2b), O(3)), one oxygen (O(6)) from the

terminal DMF molecule and one oxygen (H2(O7)) from a terminal water molecule

(Figure 7b). The Gd(2)-O distances of TDC2- ligands range from 2.3024 Å to 2.4495 Å.

The Gd-ODMF distances for Gd(1)-O(5) and Gd(2)-O(6) are 2.3732(55) Å and 2.4495(55)

Å, respectively. The Gd(2)-H2(O7) distance is 2.6447(68) Å.

The two gadolinium ions are coordinated by four TDC2- ligands to form two

different dimers (Figure 8a and 8b) along the a-axis with a distance between adjacent

gadolinium ions (Gd(1)-Gd(2)) of 5.2740(5) Å. The dimers are further bridged by two

TDC2- ligands to form a distorted chain along the a-axis, similar to framework (1) (Figure

8c).

34

(a) (b)

(c) Figure 8: (a) The Gd(1)-Gd(1) dimer formed by four bridging TDC2- linkages. (b) The

Gd(2)-Gd(2) dimer formed by four bridging TDC2- linkages. (c) A chain formed through

linking of dimers 1 and 2 down the a-axis for coordination polymer 2. The Gd

environment is shown as blue polyhedra.

35

3.2.3. Crystal structure of Eu4(2,5-TDC)6(DMF)3(H2O)2(H2O/n-prOH) (3)

Compound 3 is a neutral 3D coordination polymer that crystallizes in the

monoclinic Pc space group. The asymmetric unit contains four europium atoms, six

TDC2- ligands, three DMF molecules, two water molecules and one disordered

coordinated solvent molecule that is a 50:50 occupancy of water/n-propanol. The

europium atoms are both 8-coordinate and bound to six TDC2- ligands, one terminal

DMF molecule, and H2O molecule (Figure 9). The Eu-O bond distances for the TDC2-

ligands range from 2.2906(8) Å to 2.5126(8) Å while the Eu-ODMF distances are

2.3713(10) Å and 2.4692(10) Å, respectively. The lone water molecule (Eu(1)-O(5)-

Eu(2); distances = 2.802(1) Å and 2.5839(9) Å) bridges the two europium atoms (Eu(1)-

Eu(2)) distance = 4.7717(21) Å). The europium atoms (Eu(1) and Eu(2)) are bridged by

two TDC2- ligands and one water molecule forming a dimer along the c-axis (Figure 10a).

These dimers are further bridged by four TDC2- to form a 1D sinusoidal chain along the

c-axis (Figure 10b).

(a) (b)

Figure 9: The coordination environments around the (a) Eu3+(1) ion and (b) Eu3+(2) ion.

36

(a) (b)

Figure 10: (a) The asymmetric unit of Eu(1) and Eu(2) (pink) linked by two TDC2-

(bridging) linkages along with eight TDC2- linkages (all monodentate), two DMF

molecules and one H2O molecule (bridging) forming Eu4(2,5-

TDC)6(DMF)3(H2O)2(H2O/n-prOH) (3). (b) A chain formed through the linking of

dimers in (a) of coordination polymer 3 down the a-axis. Carboxylates are shown in red.

The slight difference in structure between coordination polymers 1, 2, and 3 can

be seen in the environments around the Ln(1) and Ln(2) ions. Also, the bidentate TDC2-

coordination mode seen in frameworks 1 and 2 is a monodentate TDC2- coordination

mode in framework 3. Finally, in frameworks 1 and 2, the lone water molecule is bonded

terminally, while in framework 3, the water molecule bridges the two europium ions. The

shorter bond distance between adjacent lanthanide ions in 3 compared to 1 and 2, allows

the water molecule to bridge the ions, instead of coordinating terminally. The overall 3D

topology of 2 and 3 are similar to that of framework 1 (Figure 4). The DMF and H2O/n-

propanol molecules occupy the channels of the networks (channel size for 2 = 6.8 X 6.8

37

Å; channel size for 3 = 6.7 X 6.7 Å). The solvent accessible void space was calculated

using PLATON122 and found to be 40.6 % for 1, compared to only 37.4 % for 2.

3.2.4. Crystal structure of Y(2,5-TDC)(DMF)2(NO3) (4)

The structure of framework 4 was solved and refined in the centrosymmetric

space group monoclinic P21/n. Each asymmetric unit contains one Y(2,5-

TDC)(NO3)(DMF)2 repeating unit to form the coordination polymer structure. Each

yttrium atom is 8-coordinate, bound to the oxygens of four TDC2- ligands, two terminal

DMF molecules and one bidentate NO3 molecule (Figure 11a). Each yttrium ion is

bridged by two TDC2- ligands to form a chain down the crystallographic a-axis (Figure

11b). These chains are further bridged through TDC2- ligands to form an overall four-

coordinate irl5 network along the crystallographic a-axis.

a) b)

Figure 11: a). A representation of the environment around the yttrium ion in coordination

polymer 4 along the crystallographic ab-plane. b) A view of coordination polymer 4

along the crystallographic a-axis.

38

0

20

40

60

80

100

120

0 100 200 300 400 500 600 700 800 900 1000

T (deg)

Wei

gh

t %

1

2

3

4

The μ2-NO3 ion and the disordered DMF molecules occupy the channels formed

by the framework. This coordination polymer is isostructural with the only other

lanthanide/TDC2- framework reported by Rosi et al.123 The nitrogen and carbon atoms of

both DMF solvent molecules are disordered over two preferred orientations and were

refined with corresponding occupancies of 52 % and 48 %. The overall 3D structure of

coordination polymer 4 is similar to that of coordination polymers 1-3.

3.3. Thermogravimetric Analysis

The stability of frameworks 1-4 was investigated using thermogravimetric

analysis under air from 40oC-900oC at a heating rate of 5oC/min (Figure 12). The

thermogram of 1 exhibits a two-step weight loss between 50 and 400oC. The first weight

Figure 12: The TGA curves of coordination polymers 1-4

loss, between 50 and 150oC, corresponds to the loss of coordinated H2O (observed 2.4 %,

expected 2.0 %). The second, between 200oC and 350oC, corresponds to the loss of two

coordinated DMF molecules (observed 14.1 %, expected 15.2 %). Between 350-375oC,

39

there is a slight weight loss possibly due to the formation of a new unknown phase. The

stability of the framework is maintained to 400oC, at which point the weight loss is rapid

and the curve is relatively flat to 900oC indicating decomposition of the structure to

lanthanide oxide sulfate (LnOSO4) which was assigned by comparing the powder

diffraction pattern with that of an authentic sample using a search/match in the EVA

program.116 Coordination polymers 2 and 3 showed similar weight losses. The first

between 60oC and 110oC corresponds to the loss of coordinated water (2; observed

1.90 %, expected 1.80 %. 3; observed 2.34 %, expected 2.60 %). The second weight loss,

between 215oC and 315oC, corresponds to the loss of two coordinated DMF molecules

(2; observed 15.0 %, expected 14.7 %.). The second weight loss in 3 corresponds to loss

of two coordinated DMF molecules and loss of coordinated n-prOH (observed 13.0 %,

expected 15.0 %). Framework 4 showed a relatively different weight loss than 1-3

because framework 4 has a lower formula weight than 1-3 and also contains a bidentate

nitrate group. The thermogram of 4 shows a two-step weight loss between 50 and 400oC.

The first weight loss, between 50 and 100oC, corresponds to the loss of residual solvent.

The second, between 200oC and 350oC, corresponds to the loss of two coordinated DMF

molecules (observed 29.1 %, expected 30.2 %). The coordination polymers decompose to

LnOSO4 (Ln = La, Gd, Eu, Y) at 900oC. The thermograms comparing the solvothermal

and reflux methods for coordination polymers 1-3 can be seen in Appendix B1-B3.

3.4. Infrared Spectroscopy

The infrared spectrum (Figure 13) of coordination polymer 1 exhibits a broad

peak at 3500 cm-1 which is characteristic of the O-H stretch of the water molecule. The

40

0

20

40

60

80

100

120

050010001500200025003000350040004500

Wavenumber (cm-1)

Tra

nsm

itta

nce

%

1a

1

weak vibrations near 3097 cm-1 and 2935 cm-1 correspond to the C-H stretching modes of

the methyl groups of DMF, the ring protons of 2,5-TDC, and the C-H stretching mode of

the aldehyde group on the DMF molecule. The stretching frequency for the carbonyl

group on the thiophene ring of 2,5-TDC, normally seen at 1662 cm-1, was not observed

after coordination to the lanthanide metal, indicating complete deprotonation of 2,5-TDC

to 2,5-TDC2- in both frameworks 1 and 2.124 The asymmetric and symmetric stretching

modes for the carboxylate groups on the thiophene ring occur at 1541-1525 cm-1 and

1398-1372 cm-1. The DMF C=O stretch can be seen at 1666 cm-1, the in-plane and out-

of-plane bending modes of the thiophene ring at 1036 cm-1 and 769 cm-1, and the ring

deformation at 801 cm-1.

Figure 13: The infrared spectra of coordination polymer 1 at room temperature (RT) and

after heating to 380oC (compound 1a).

A comparison of the IR spectra of compound 1 at RT and after heating to 410oC is

shown in Figure 13. The characteristic DMF C-H aldehyde stretch and C=O stretch at

no DMF C-H aldehyde or DMF C=O aldehyde stretch in 1a.

41

0 1 0 2 0 3 0 4 0 5 0 6 0

0

1 0 0

2 0 0

3 0 0

4 0 0

Inte

nsity

2 d e g re e

R T

3 8 0 oC

9 0 0 oC

2932 cm-1 and 1666 cm-1 which are apparent at room temperature, are no longer seen

after heating to 380oC, indicating loss of DMF from the channels. The metal-carboxylate

(M-O-C) asymmetric and symmetric stretching vibrations at 1525 cm-1 and 1382 cm-1 are

still present along with the C-H stretches of thiophene ring protons at 3087 cm-1, the in-

plane and out-of-plane bending modes of the thiophene ring (1036 cm-1 and 776 cm-1)

and the ring deformation also (816 cm-1). Similar results are seen for coordination

polymers 3-4 when heated to temperatures between 350-410oC.

Figure 14: X-ray powder diffraction spectra comparing the room temperature pattern to

the patterns at 380oC and 900oC of coordination polymer 1.

Figure 14 shows a powder diffraction comparison of framework 1 at room

temperature, when heated to 380oC, and when heated to 900oC. Peaks at 2θ = 24o and 34o

at 380oC support the conclusion from the thermogravimetric analysis section, that their is

a formation of a new phase between 350-375oC. The peak at 2θ = 11o for the RT powder

pattern of (1) shifts to 2θ = 12o at 380oC indicating a smaller d-spacing. The Miller

indices for this peak are dhkl = 1,1,1. The plane passes at a diagonal through the channels

42

of the framework. This indicates that the shift to smaller d-spacing occurred because the

solvent was removed from the channels of the framework causing the unit cell to shrink

slightly. These results are in agreement with the conclusion that the DMF molecules can

be removed from the channels with retention of the overall framework. The powder

pattern at 900oC was compared to known patterns in the inorganic crystallographic

database and confirmed the decomposition of the framework to LnOSO4 (Ln = La, Gd,

Eu, Y).

3.5. Solid State Photoluminescence

The solid state photoluminescence spectrum of the europium compound 3 was

taken at room temperature and can be seen in Figure 15. When excited at 392 nm,

compound 3 emits a red luminescence (Figure 15c). The emission peaks are attributed to

the 5D0-7Fn (where n =1, 2, 3, 4) transitions. The peaks appear at 591, 617, 651 and 698

nm with the strongest emission attributed to the 5D0-

7F2 transition at 617 nm. The 5D0-7F2

electric-dipole transition is sensitive to the coordination environment around the

europium ion and is almost twice the intensity of the 5D0-7F1 transition (a magnetic dipole

transition relatively insensitive to the coordination environment) which indicates that the

europium ion does not sit on an inversion center. The enhanced luminescence of the

framework 3 is most likely attributed to the rigidity of the framework, which reduces the

loss of non-radiative energy through bonds.125-127

43

500 600 700 800 900

20000

40000

60000

80000

100000

120000

140000

160000

180000

5D0

5D0

5D0

7F4

7F3

7F2

Inte

nsi

ty

W avelength (nm)

5D0

7F1

(a)

(b) (c)

Figure 15: (a) Excitation (inset) and emission spectra of coordination polymer 3 at

excited at 390 nm. (b) Coordination polymer 3 under visible light (c) Coordination

polymer 3 under UV light (long wavelength)

3.6. Catalytic Properties

The following section was not published in J. Chem. Cryst. 2010, 40, 222, as the

previous sections were. The heterogeneous catalytic properties of coordination polymer 1

were assessed using an organic reaction known as the Biginelli reaction (Scheme 4).106

200 250 300 350 400 450 500

wavelength (nm)

Inte

ns

ity

(a

.u.)

44

R1

O

H+

H2N NH2

O

+O

O

O R1

NH

HN O

O

O+ H2O

R1 = aryl

CP 1a

Toluene or MeOH110oC, 1hr

Scheme 4: The Biginelli reaction using CP 1a as a heterogeneous catalyst.

Compound 1, was evacuated in the oven at 250oC for 1 hour to give the activated catalyst

1a and then stored immediately under argon until use. The results of the catalytic

experiments are shown in Table 1. A solid product was isolated after the reaction. The

yield of dihydropyrimidinone product was calculated based on the ratio of product to

starting material. The area under the product peak was compared to the area under the

starting material peak in the GC-MS trace. The control used for this experiment was

Yb(OTf)3, which showed good conversion to the dihydropyrimidinone 10a under reflux

conditions (50 %). The proposed mechanism for the Biginelli reaction using a Lewis acid

catalyst is shown in Scheme 5. The evacuated catalysts 1a and 2a gave low yields (10-

25 %) of dihydropyrimidinone 10a under reflux conditions in either toluene or methanol.

The activated catalysts showed similar yields for dihydropyrimidinone 10b in either

toluene or methanol. It’s interesting to note, there was no catalytic activity when stirred at

room temperature for 3 days in reactions involving both 1a and 2a. This could be

attributed to the organic linker being slightly basic, making the lanthanide ion not as

electropositive.

45

Table 1: Catalytic syntheses of dihydropyrimidinones using CP 1a and 2a under different

reaction conditions.a

________________________________________________________________________

R1 Solvent Catalystb Product Yield (%) Temperature

d

________________________________________________________________________ C6H5 toluene none 10a 0 110 C6H5 toluene Yb(OTf)3 10a 49 110 C6H5 none Yb(OTf)3 10a 55 110 C6H5 toluene 1a 10a 21 110 C6H5 MeOH 1a 10a 11 110 C6H5 toluene 2a 10a 21 110 C6H5 MeOH 2a 10a 21 110 C6H5 none 2a 10a 16 110 C6H5 toluene 1a* 10a 0 RT C6H5 MeOH 1a* 10a 0 RT C6H5 toluene 2a* 10a 0 RT C6H5 MeOH 2a* 10a 0 RT ________________________________________________________________________

3-thienyl toluenec 1a 10b 14 110

3-thienyl MeOHc 1a 10b 10 110


3-thienyl MeOHc 2a 10b 18 110

________________________________________________________________________ a For Yb(OTf)3; 1 mL, reflux, 5 hr. For 1-2; 0.2 mL, 110oC, 1 hr. b 5 mol % MOF 1-2; a = framework activated at 250oC. * room temperature, 3 days.

c 1.0 mL, 110oC, 1 hr.

d temperature in oC.

46

EtO

O R1

NH

OH3C OH2N

R1 H

O

R1 H

O

H2N NH2

O+

MOF 1a

H2N NH

O

R1 OH

-H2O

HH2N N

O

R1 H

MOF 1a

NLn

H2N

O

R1H

EtO

O CH3

O

H+EtO

O R1

NH

NH

H3C OHO

-H2OEtO

O R1

NH

NH

H3C O

10a

MOF 1a

Scheme 5: The proposed mechanism for the Biginelli reaction using an activated

coordination polymer as a heterogeneous catalyst.

3.7. Conclusion

Four new lanthanide-thiophenedicarboxylate coordination polymers, 1-4, were

synthesized using both a solvothermal and reflux method. Both methods can be used to

produce the same frameworks as shown by x-ray powder diffraction. Single crystal x-ray

diffraction indicated that metal-carboxylate bonds form slightly different dimers for 1-4,

while the 2,5-TDC acts as the linker to form neutral three dimensional 4,4-nets with

diamond shaped channels. Thermogravimetric analysis and IR spectroscopy indicated

removal of solvents (DMF and H2O) from the channels up to 400oC, above which

decomposition of the framework ensued to give LnOSO4 (Ln = La, Gd, Eu, Y). Powder

diffraction data indicated that the 3D structure remained intact with a small contraction in

at least one cell parameter. The catalytic activity of 1a and 2a was assessed in the

Biginelli reaction. The homogeneous control catalyst, Yb(OTf)3, showed the best

47

catalytic activity. There was limited activity for the activated catalysts 1a and 2a (10-

25 %) at reflux temperature in either MeOH or toluene. The catalysts showed no activity

when stirred at room temperature for 3 days. Catalysis was found to be occurring on the

surface of the coordination polymers which is in accord with the inability of the product

to fit in the channels of the framework.

Due to the success in forming coordination polymers 1-4 using the solvothermal

and reflux methods, the same methods were considered for the synthesis of

tetrafluorobenzene-1,4-dicarboxylic acid/lanthanide-based MOFs. The need for a more

acidic linker like tetrafluorobenzene-1,4-dicarboxylic acid, as opposed to 2,5-TDC, was

imperative. These fluorine atoms should increase the electron-withdrawing power of the

linker and make the lanthanide centers more electropositive, which will make them better

Lewis acids and help increase the catalytic activity of the ensuing frameworks.

Utilization of the solvothermal method, which was employed for the synthesis of

coordination polymers 1-4, gave no product in the case of coordination polymers 5-9.

Once the temperature was increased from 105oC to 145oC and the heating was extended

from 24 to 48 hr, a crystalline product was obtained. We concluded, based on the single

crystal x-ray diffraction data, that the single crystals were of the starting material

Tb(NO3)3. In order to synthesize coordination polymers 5-9 with tetrafluorobenzene-1,4-

dicarboxylic acid, a different tactic was employed which is discussed in the next section.

48

CHAPTER 4

SYNTHESIS, CRYSTAL STRUCTURE AND PROPERTIES

OF COORDINATION POLYMERS 5-9

Christopher M. MacNeill, Cynthia S. Day, Amy Marts, Abdessadek Lachgar and Ronald

E. Noftle

The following chapter was published as a manuscript in the journal Inorganica Chimica

Acta, 2011, volume 365, pages 196-203, and is reprinted with permission from the

journal. All of the research presented was conducted by Christopher M. MacNeill with

help from Amy Marts. Crystal Structure Data was compiled by Cynthia S. Day. The

manuscript was prepared by Christopher M. MacNeill and edited by Abdessadek Lachgar

and Ronald E. Noftle

49

4.1. Synthesis of Coordination Polymers 5-9

Initially, a solvothermal method was employed at varying temperatures (100, 120

and 145oC) from 18-48 hours in an array of different solvent systems without adjustment

of pH; however, crystals suitable for single-crystal X-ray diffraction were not obtained.

The synthesis of coordination polymers 5-9 was carried out by a vapor diffusion method

which resulted in precipitation of high purity samples. Stoichiometric ratios of 1:1

lanthanide metal to H2F4BDC were utilized for all syntheses, and, in all cases, the same

framework resulted, as indicated by single crystal and powder x-ray diffraction. N,N-

Diethylformamide (DEF) was the preferred solvent since use of DMF resulted in

microcrystalline products. Ethanol was chosen as a co-solvent because enhanced crystal

growth resulted compared to use of DEF/H2O, DEF/MeOH, and DEF/n-propanol

mixtures. The bound solvent cannot be removed at RT, but the compounds tend to lose

lattice DEF upon exposure to air and under vacuum. This is reflected in the analytical

results which show varying amounts of remaining DEF in the lattice.

Five new isostructural two-dimensional lanthanide-based coordination polymers

with the formula Ln2(F4BDC)3(DEF)2(EtOH)2 · 2(DEF) (Ln = Tb, 5; Gd, 6; Eu, 7; La, 8;

Nd, 9; F4BDC2- = 2,3,5,6-tetrafluoro-1,4-benzenedicarboxylate ligands; DEF = N,N’-

diethylformamide), have been synthesized by reaction of Ln(NO3)3 and H2F4BDC in a

DEF/EtOH solvent mixture. The compounds were characterized by single-crystal and

powder X-ray diffraction. Compounds 5-9 were further characterized using thermo-

gravimetric analysis and infrared spectroscopy. Studies of the photoluminescence

properties of compounds 5 and 7, as well as the catalytic activity of compounds 7-9 in the

Biginelli reaction, are presented.

50

4.2. Single Crystal X-Ray Diffraction

4.2.1. Crystal Structure of Tb2(F4BDC)3(DEF)2EtOH2 · 2(DEF) (5)

Coordination polymer 5 crystallizes in the monoclinic space group C2/c. The

carboxylic acid moieties are completely deprotonated and the framework forms an

overall 2D structure. The asymmetric unit contains one terbium ion, one and a half

F4BDC2- molecules, one terminal DEF molecule, one EtOH molecule and one lattice

DEF molecule (Figure 16a). There are two asymmetric units contained in each formula

unit. Each terbium ion is 9-coordinate with two bridging F4BDC2- oxygen atoms (O(1)

and O(2)), two bidentate F4BDC2- molecules (O(3), O(4)), one μ3-F4BDC2- molecule

(O(5), O(6)), one oxygen (O(7)) from the terminal DEF molecule and one oxygen (O(8))

from the terminal EtOH molecule. The lattice DEF oxygen (O(9)) is hydrogen bonded to

the hydrogen on the sp2 carbon on the coordinated ethanol molecule. The TbO9 polyhedra

can be described as tri-capped trigonal prisms. The terbium atoms are linked through the

oxygen atoms from two bridging F4BDC2- ligands (O(1), O(2)), and two μ3-F4BDC2-

ligands (O(5), O(6)) to form a dimer (Figure 16b and 16c).

The Tb(1)-Tb(1) distance is 4.1450(4) Å. All of the Tb-O distances from the

F4BDC2- range from 2.319(2) Å to 2.478(2) Å, which corresponds well to known

terbium-oxygen bond distances.128-129 The hydrogen bond distance from the lattice DEF

molecule to the ethanol molecule is 1.87(5) Å.

51

a) b)

c)

Figure 16: a) A view of the contents of the asymmetric unit for

Tb2(F4BDC)3(DEF)2(EtOH)2 · 2(DEF) (5). Hydrogen atoms have been omitted for

clarity. (b) A view of the formula unit of 5 with two identical terbium atoms. (c) A view

of the formula unit of 5, where the contents of the polyhedra represent the terbium atoms.

The dimers are further bridged through six F4BDC2- linkers (Figure 17a) to other dimers

to form an infinite two-dimensional sheet along the bc-plane (Figure 17b). The sizes of

the rhombic channels are 11.5 X 11.5 Å based on the distance between terbium atoms.

Each two-dimensional sheet is stacked to form a 3D layered topology along the a-axis

52

(Figure 18a-b). The DEF and ethanol molecules are trapped in the layers between the 2D

sheets, which have a size of 12.9 Å (Ln-Ln distance).

a) b)

Figure 17: a) A view of the dimer of 5 connected to other dimers through six F4BDC2-

linkages. (b) A view of (a) forming an overall 2D sheet with solvent molecules and

hydrogen atoms omitted for clarity.

a) b)

Figure 18: (a) A view of the 2D sheet of coordination polymer 5 along the b-axis. (b)

formation of a 3D layered topology from stacking of the infinite 2D sheets from (a).

lattice DEFs were omitted for clarity.

11.5 Å

11.5 Å

12.9 Å

53

4.2.2. Crystal Structures of Gd2(F4BDC)3(DEF)2EtOH2 · 2(DEF) (6), Eu2(F4BDC)3-

(DEF)2EtOH2 · 2(DEF) (7), La2(F4BDC)3(DEF)2EtOH2 · 2(DEF) (8) and

Nd2(F4BDC)3-(DEF)2EtOH2 · 2(DEF) (9)

Coordination polymers 6-9 crystallize in the same space group as coordination

polymer 5, monoclinic C2/c. The carboxylic acid moieties are completely deprotonated

and the frameworks form an overall 2D structure that is isostructural with framework 5.

The x-ray powder diffraction data comparing the simulated pattern to the as-synthesized

patterns for these frameworks can be seen in Appendix B8.

4.3. Thermogravimetric Analysis

The thermal stability of compounds 5-9 was investigated using thermogravimetric

analysis by heating the samples in air to 900oC at a heating rate of 5oC/min (Figure 19).

In the case of compound 5, there was a loss of two coordinated EtOH molecules between

40-115oC, followed by loss of two lattice DEF molecules from 115-200oC (calc. 19.3 %

exp. 19.2 %). A final weight loss of two coordinated DEF molecules occurred between

250-325oC (calc. 13.2 % exp. 13.0 %). The compound is stable to 250oC and begins to

decompose at 325oC to give terbium oxyfluoride (TbOF) at 900oC as determined by

PXRD.116 Similar solvent losses were observed for compounds 6-9.

54

0

20

40

60

80

100

120

0 100 200 300 400 500 600 700 800 900 1000

Temperature (oC)

Wei

gh

t %

56789

Figure 19: The TGA curves of coordination polymers 5-9.

4.4. Infrared Spectroscopy:

The infrared spectra of 5-9 were measured between 400 and 4000 cm-1 (Appendix

B7). The IR spectrum of 7 shows a broad band at 3450 cm-1 which corresponds to the O-

H stretch of the ethanol. The weak vibrations at 2989 cm-1 and 2950 cm-1 correspond to

the DEF C-H methyl and DEF C-H aldehyde stretching modes. The stretching frequency

for the carbonyl group on the benzene ring, normally in the range of 1680-1720 cm-1, was

lowered after coordination to the lanthanide metal ion. The asymmetric and symmetric

stretching modes for the bound carboxylate groups occur at 1623 cm-1 and 1411 cm-1.

The DEF C=O stretch can be seen at 1660 cm-1. After heating to remove solvent from the

lattice, the IR spectrum of compound (7a) was taken. The spectrum shows that the DEF

C-H aldehyde and DEF C-H methyl stretches are no longer apparent, which indicates that

55

the DEF can be removed from the lattice and activated before its use in the catalytic

experiments (Figure 20).

Figure 20: The infrared spectra of coordination polymer 7 (as synthesized) and

coordination polymer 7a (after evacuation to remove solvent from the lattice).

4.5. Solid State Photoluminescence:

The room temperature solid state photoluminescence spectra for 5 and 7 were

taken and can be seen in Figure 21. Upon excitation, 5 emits a green luminescence. The

transitions appear at 489, 544, 585 and 620 nm and are attributed to the 5D4-7Fj (J =

6,5,4,3) bands.130-132 The 5D4-7F5 transition (hypersensitive) is the most intense peak and

the 5D4-7F6 transition is second in intensity consistent with other Tb-based systems.133

Compound (7) emits a red luminescence. The emission peaks which appear at 590, 615,

05001000150020002500300035004000

wavenumber (cm-1)

Tra

nsm

itta

nce

(7)

(7a)

no DEF C-H methyl or DEF C-H aldehyde stretch in 7a.

56

450 500 550 600 650 700 750

Wavelength (nm)

Re

lati

ve

Inte

nsi

ty (

a.u

.)

5D0

5D0

5D0

5D0

7F1

7F2

7F3

7F4

Eu2(F4BDC)3(DEF)2(EtOH)2-2(DEF) (3)

350 400 450 500 550 600 650

Wavelength (nm)

Rel

ativ

e In

ten

sity

(a.

u.)

5D4 7F6

5D4

5D4

5D4

7F5

7F4

7F3

Tb2(F4BDC)3(DEF)2(EtOH)2-2(DEF) (1)

650 and 695 nm are attributed to the 5D0-

7Fj , (J = 1,2,3,4) transitions respectively, with

the strongest emission attributed to the 5D0-

7F2 transition at 615 nm.

a) b)

c) d)

Figure 21: (a) A picture of Tb 5, Eu 7 and La 8 coordination polymers under visible light.

(b) A picture of Tb 5, Eu 7 and La 8 coordination polymers under UV light. (c) The solid

state photoluminescence spectrum of Eu 7 excited at 392 nm. (d) The solid state

photoluminescence spectrum of Tb 5 excited at 300 nm.

57

The appearance of the broad, low intensity, forbidden 5D0-7F0 transition indicates that the

metal is in a non-centrosymmetric ligand field. The 5D0-7F2 electric-dipole transition is

sensitive to the coordination environment around the europium ion and is almost twice

the intensity of the 5D0-7F1 transition (a magnetic dipole transition relatively insensitive to

the coordination environment) which again indicates that the europium ion does not sit on

an inversion center. This information was helpful in the crystal structure analysis.134-136

4.6. Catalytic Properties:

Lanthanide triflate salts are the most widely used homogeneous Lewis acid

catalyst in the Biginelli reaction, giving yields of >80 % in a number of solvents, under a

range of conditions, and using a variety of different starting reagents.137 Lanthanide

triflates, however, are difficult to recover because excess solvent must be removed and

the triflates must be dried under vacuum for several hours. The Biginelli reaction has

been used to assess the Lewis acid catalytic properties of HIOMs by other groups.138-140

However; their syntheses were carried out at room temperature and take 2-3 days. In light

of this fact, we explored the catalytic activity of the compounds reported here under a

shorter time period (1.5 hr) and a longer period (3 days) under different conditions of

temperature. Compounds 7-9 all gave similar yields so we chose to focus on compound 7

for our study.

The catalytic activity of 7 and its activated catalyst 7a, from which solvent had

been removed, were compared and the results are presented in Table 2. Compound 7 is

interesting in that it is insoluble in everything except water, so its homogeneous catalytic

activity in water as well as its heterogeneous activity in toluene and methanol was

58

investigated. The europium catalyst gave greater than 50 % of the yield observed for

Yb(OTf)3 but at a lower temperature (70oC) in about 30 % of the time. In the case of

heterogeneous reactions, the catalyst was easily recovered and re-used without loss of

activity (Appendix B9-B10).

Table 2: Catalytic syntheses of dihydropyrimidinones using CP 7, 7a, 8 and 9 under

different reaction conditions.a

________________________________________________________________________

R1 Solvent Catalystb Product Yield (%) Temperature

d

________________________________________________________________________ C6H5 toluene none 10a 0 110 C6H5 toluene Yb(OTf)3 10a 49 110 C6H5 none Yb(OTf)3 10a 55 110 C6H5 toluene 7 10a 28 70 C6H5 MeOH 7 10a 33 70 C6H5 toluene 7a 10a 38 70 C6H5 MeOH 7a 10a 39 70 C6H5 toluene 7* 10a 10 RT C6H5 MeOH 7* 10a 21 RT C6H5 H2O 7* 10a 41 RT C6H5 toluene 7a* 10a 12 RT C6H5 MeOH 7a* 10a 19 RT C6H5 H2O 7a* 10a 37 RT ________________________________________________________________________

3-thienyl toluenec 7 10b 13 70

1-napthyl toluenec 7 10c 12 70


1-napthyl toluenec 7a 10c 9 70

________________________________________________________________________ C6H5 toluene 8 10a 28 70 C6H5 toluene 9 10a 27 70 ________________________________________________________________________ a For Yb(OTf)3; 1 mL, reflux, 5 hr. For 7-9; 0.2 mL, 70oC, 1.5 hr. b 5 mol % MOF 7-9; a = framework activated at 150oC. * room temperature, 3 days.

c 1.0 mL, 70oC, 1.5 hr.

d temperature in oC.

59

At room temperature over three days, reactions in water give higher yields of

dihydropyrimidinone, comparable to those of Yb(OTf)3, as would be expected for

homogeneous catalysis. To determine whether catalysis was occurring in the layers or on

the surface of the framework, we compared the catalytic activity of the activated catalyst

7a to 7.

The activated catalyst gave somewhat higher yields at 70oC than did the

unactivated catalyst. This may be due to the greater availability of the Lewis acid sites on

the lanthanide metal because of the removal of coordinated solvent molecules from the

framework. There was no significant difference at room temperature. Aldehyde reactants

of different sizes (3-thiophenecarboxaldehyde, 5.7 Å; benzaldehyde 6.1 Å; 1-

napthylcarboxaldehyde, 7.9 Å)141 were chosen to see if catalytic activity decreased as the

size of the reactant increased. The distance between the layers in (7) is 7.4 Å (based on

Eu(1)-Eu(1) distance). The yields of the corresponding dihydropyrimidinones at 70oC

were similar for the different aldehydes (10b, 13 %; 10c, 12 %) indicating a constant

activity, regardless of size. These results suggest that catalysis occurs at the surface and

not between the layers. Finally, the catalyst was finely ground to increase surface area. If

catalysis were taking place on the surface, as the surface area increased, the yield of the

Biginelli product should also have increased. A modest increase in Biginelli product was

observed (7-10 %) consistent with the conclusion that catalysis occurs on the surface.

Compounds 8 and 9 gave yields comparable to those obtained for 7 at 70oC for 1.5 hr.

4.7. Conclusion

Five new 2D lanthanide-based coordination polymers incorporating 2,3,5,6-

tetrafluoro-1,4-benzenedicarboxylate have been synthesized using a vapor diffusion

60

method and characterized by single crystal x-ray diffraction, powder diffraction, infrared

spectroscopy and thermogravimetric analysis. The framework consists of lanthanide

metal ions linked by [F4BDC]2- ligands to form 2D sheets, which stack to form a layered

topology with solvent molecules between the sheets. DEF and EtOH can be removed

from the layers with full retention of the framework upon heating to 150oC. Compounds

5 and 7 showed photoluminescent properties upon excitation at 392 nm and 350 nm,

respectively. Compounds 7-9 showed catalytic activity in the Biginelli reaction. The

increase in temperature from RT to 70oC provided a more rapid synthesis (1.5 hr vs. 3

days) compared to previous methods.142-143 Evidence suggests that the catalysis is taking

place at the surface of the framework and not within the layers of the framework.

61

CHAPTER 5: INTRODUCTION 5.1 The Environment

At the rate of present consumption of fossil fuels and the strain it puts on the

environment, it is only a matter of time before we have to rely on other energy sources.144

Currently, 80% of energy comes from fossil fuels such as coal, oil and gas.145 Fossil fuels

are of limited supply and the price of oil is increasing rapidly, so the need to move to an

alternative energy source is looming. Solar energy is of unlimited supply and is a clean

and renewable energy source. We receive 3.9×1024 J of energy from the sun annually. In

2004, the world energy consumption was 4.7×1020 J. This means in one hour, we can

supply the entire world with enough energy to fulfill our yearly demand.146-147Grid-

connected organic photovoltaic modules can now be installed on the roofs of houses and

the windows of buildings. However, the cost of such undertakings is still too high. For

the past thirty years, the cost of organic-based photovoltaics has continuously

decreased.148 Currently, depending on country and availability, the price of small cell

organic solar modules is anywhere between 8-12 US$/W with efficiencies between 1-3%

and lifetimes under 2 years. The future cost of organic solar cells should decrease, while

improvements in solar cell lifetime and efficiency should increase. By 2025, solar cell

lifetimes should improve to 5-7 years, with efficiencies between 5-9 % at a cost of 0.5

US$/W. 149

62

5.2 History of Photovoltaics

5.2.1 Photoelectric effect

Before introducing the history of inorganic and organic photovoltaic cells, a brief

history of the photoelectric effect will be introduced. The definition of the photoelectric

effect is when a material absorbs light of short wavelength, such as visible or ultra-violet,

and electrons are emitted from the material.150 Hertz coined this term in the late 1880’s

when he discovered the phenomenon.150-151 The understanding of the photoelectric effect

opened the door to an understanding of how electrons move under electromagnetic

radiation. Albert Einstein demonstrated a mathematical relationship between energy and

frequency when he described light as photons and not as waves.152-153 He theorized that if

a photon has energy above the threshold frequency, then a single electron can be ejected

(E = hυ). He later won the Nobel prize in physics in 1921 for this work.

The photovoltaic (PV) effect was first observed by Alexandre Becquerel in 1839.

He showed a relationship between light and the electronic properties of materials, while

illuminating an aqueous solution containing two platinum electrodes covered in silver

bromide and silver chloride.154 It wasn’t until 30 years later between 1873 and 1876, that

Willoughby Smith along with William Adams, discovered that selenium can be

photoconductive.155-156 Up to the 1940s, research on new photoconducting materials,

based on selenium, copper, thalium and lead, was underway.157-162

5.2.2 Inorganic Photovoltaics

The first thin film solar cell based on elemental selenium was realized in the

1880’s by the work of Fritts.163 He coated a selenium semiconductor with gold and

63

achieved an efficiency of 1%. Russell Ohl holds the first solar cell patent (US Patent

2402662) and in 1939, discovered the p-n junction by investigating impurities in

crystals.164 It was not until the 1950s that commercialization of inorganic solar cells was

initiated. Bell laboratories produced the first inorganic solar cell made of crystalline

silicon and it had a power conversion efficiency (PCE) of 6%.165 Since then, crystalline

silicon-based solar cells have dominated the photovoltaic market, reaching efficiencies of

24 %, near their theoretical upper limit of 30 %.166-170 Silicon-based cells are known as

“first generation” solar cells. Silicon is abundant, making up 20 % of the earth’s crust and

solar cells constructed from silicon can typically last 25-30 years, when fabricated into a

device. However, these cells require a large area, and are very labor-intensive to

produce.171 Currently, some first generation solar cells have been replaced by a “second

generation” technology based on thin film/semi-conductors. These materials include

cadmium telluride (CdTe), copper indium gallium selenide (CIGS) and amorphous

silicon.172 Second generation photovoltaic efficiencies range from 5-20 %. The best

known efficiency of an amorphous silicon based cell is 9.4 % with a cost of 1-2 US$/W.

For CdTe and CIGS, PCEs of 16.7 % and 19.4 % have been realized with a cost of 2 -2.5

and 1 US$/W.173-174 For the past fifteen years, a trend to move from “second generation”

thin film/semiconductors to “third generation” organic-based solar cells is proceeding.

This is due to the need for a technology that is low cost, flexible, easily manufactured and

very efficient. Since second generation solar cells can now be made on a large scale and

cost has decreased to around 1 US$/W, this makes the potential for cost reduction of

organic solar cells a future reality.

64

5.2.3 Organic Photovoltaics

The first organic molecule to show photoconductivity was anthracene in the early

1900’s.175-176 Interest in organic molecules was growing during this time period, which

led to research on organic molecules as potential photoconductors. Common dyes, such

as methylene blue and biological molecules, such as chlorophyll and porphyrins, were

found to exhibit the PV effect during the 1950s-1960s.177-178 Polymeric materials were

first thought to be insulating; however, it was found that they can exhibit semi-

conducting or even metallic properties.

Conjugated polymers are materials that are completely sp2 hybridized. Because of

this, the p-orbitals overlap and an electron can be delocalized along the chain. This

overlap and delocalization allows for charge to be shuttled along the backbone leading to

interesting electrical and optical properties. One of the first reports of a conducting

polymer was poly(vinyl carbazole).179 This was later followed up by the pioneering work

of Heeger on poly(acetylene) films.180-181 Their group found that if you doped

poly(acetylene) with iodine, the conductivity increased 108 fold. The first solar cell

device made with poly(acetylene) came from Weinberger and co-workers.;182 however,

the cell had a very low Voc (0.3 V). During the early 1980’s, polythiophenes were

investigated for their PV applications.183 The limitation again was the Voc and the

quantum efficiency. Finally in the early 1990’s, poly(phenylene-vinylene) cells showed a

high Voc (1 V) and a PCE of 0.1 %.184 The first report of a solar cell using a conjugated

polymer as a donor and a fullerene acceptor was reported by Heeger and co-workers in

the mid 1990’s.185-187 The cell was based on poly(2-methoxy-5-(2’-ethyl-hexyloxy)-p-

phenylene-vinylene) (MEH-PPV). However, this polymer was not easily processable and

65

the band-gap was too large. Power conversion efficiencies (PCE) for MEH-PPV/C60

systems could only reach PCEs of 3 % overall. It was not until 2002, that poly(3-

hexylthiophene) (P3HT) polymers with C60 gave the most encouraging results.188 Since

then, the potential for polymer-based photovoltaics has increased substantially with some

polymer/fullerene composites reaching a PCE of close to 5 %.189-190 However, a PCE of

5% still is not good enough to compete with silicon technologies. Development of new p-

type conjugated polymers that can reach 10 % efficiency191-192 are needed and the

synthesis of these polymers will play a pivotal role in driving the future of this field.

Insight into new donor-acceptor copolymers for organic solar cell applications will be

discussed in Chapters 7-9 of this text.

5.3 Theory and Device Physics of Organic Solar Cells

The fundamental steps of polymer solar cell operation193 are as follows (Figure

22). 1.) light passes through the ITO substrate and is absorbed by the donor polymer. 2.)

an electron is promoted from its highest occupied molecular orbital (HOMO) to its lowest

unoccupied molecular orbital (LUMO). This forms a coulombically bound electron/hole

pair, also known as an exciton. This exciton then travels along the polymer backbone

diffusing towards the donor/acceptor interface where there is a drop in potential energy.

Ideally, this distance would be around 5-20 nm for most semi-conductors.194-196 3.) the

electron is transferred from the LUMO of the donor polymer to the LUMO of the

acceptor material. 4.) each charged species now has to diffuse through the device towards

their respective electrodes. The hole travels towards the anode while the electron travels

towards the cathode. Once the charge reaches the contacts, the photon to electron process

66

Figure 22: A schematic representation of the steps involved in generating photocurrent in

a donor-acceptor polymer solar cell device.

is complete. In some cases, once the exciton is produced, the charges may re-combine

and give off a photon. At this point, the ability to generate a photocurrent will cease. A

donor polymer with low ionization energy and an acceptor with a high electron affinity

would be ideal for organic photovoltaic applications. Here are a few terms one may come

across when accessing a polymer-based solar cell material.

5.3.1. Open Circuit Voltage (Voc)

The open circuit voltage of a device is defined as the difference in electrical

potential between the anode and the cathode when there is no external connection, i.e. the

circuit is open. It is known as the maximum voltage for a solar cell and occurs when no

current is flowing. The Voc can also be considered as the difference in work functions

between the two metal contacts in the cell.197 If there is not a good overlap of the orbitals

on the metal with the orbitals of the polymer, there can be charge carrier loss and the Voc

67

Voc = Eg 1 -T s

T c(0)

will decrease. Theoretically, the Voc can be estimated by the difference in voltage

between the HOMO of the donor material and the LUMO of the acceptor material in

volts.198-199 The Voc of a material tends to increase with increasing band-gap according to

an equation outlined by Baruch and co-workers.200 Vocs of 0.7 V or higher are ideal for

solar cell applications.

Equation 1: An equation relating the band gap (Eg) of a polymer to the open circuit

voltage (Voc) by Baruch and co-workers.200

5.3.2. Short Circuit Current Density (Jsc)

The short circuit current density is the maximum current of a solar cell in which

the impedance is low and the voltage is zero. The short circuit current depends on many

factors associated with the solar cell such as the optical properties of the materials, the

charge carrier lifetime, and the area of the cell.

5.3.3. Fill Factor (FF)

The FF is defined as the ratio of the maximum power of the solar cell to the

theoretical obtainable power of the cell. The FF can also be defined as the ratio of the

number of charge carriers reaching the electrodes compared to those recombining,

expressed as a percentage. When an exciton is generated, it has to migrate to the acceptor

molecule and transfer its charge. Once the charge is transferred, the electron hops

towards the cathode, while the hole moves towards the anode. The exciton diffusion

68

length can play an important role in obtaining a large FF. If the diffusion path of the

exciton is too long (>10 nm), the charges will recombine and the FF will be dramatically

decreased. Generally, a FF of at least 65 % is required for the cell to potentially achieve

10 % PCE.198 The fill factor can be improved by adding an electron transport layer to the

electrode such as lithium fluoride (LiF)201-203 or a hole transport layer such as

polyethylenedioxythiophene: polystyrenesulfonate (PEDOT:PSS).204 By using a bulk

heterojunction device, where donor and acceptor are blended together, the diffusion of

the exciton will be less than 10 nm and an optimum fill factor will be obtained. The FF

tells how well the solar cell is working. Typically, FFs for a good organic photovoltaic

cell are between 0.5-0.7. A graph of the J-V curve of a solar cell under solar illumination

is seen in Figure 23.

Figure 23: A J-V curve (black) of a BHJ solar cell under illumination. Characteristic

open circuit voltage (Voc), short circuit current (Jsc) and FF (Area A/Area B), as well as

the calculation of power conversion efficiency (PCE) are indicated on the figure.

69

5.4 Device Architectures of Organic Solar Cells

There are three types of polymer-based solar cell devices; the bi-layer device, the

bulk-heterojunction (BHJ) device and the tandem solar cell device (Figure 24). A bi-layer

device is comprised of a hole-type donor material lying on top of an electron acceptor

material.205-207 The limitation of this device architecture is that the sizes of hole donor

material and the electron acceptor material are generally greater than the exciton

diffusion length (5-12 nm)208 of the generated hole/pair. If the exciton is not successfully

transferred to the acceptor material, the exciton recombines and the photocurrent is lost.

(a) (b) (c)

Figure 24: A representation of (a) a bi-layer solar cell device, (b) a BHJ solar cell device

and (c) a tandem solar cell device

A BHJ device is different from a bi-layer device in that the donor and acceptor materials

are blended together in a single layer. This gives greater external quantum efficiency to a

BHJ device compared to bi-layer device due to the presence of a single active layer as

opposed to a bi-layer where the interface between the layers is known to erode with

time.209 This architecture also helps prevent recombination of the exciton because the

acceptor material is now within the exciton diffusion length. A tandem solar cell consists

of a blend of two or more polymers separated by a thin charge carrier layer and connected

70

in series.210 One sub-shell (bottom device) can be made up of a certain polymer blend that

absorbs in the blue region of the visible spectrum, while the second sub-shell (top device)

can be made up a blend that absorbs in the red region of the spectrum. Together, these

two sub-shells connected make up a cell that absorbs over most of the visible region

making use of more sunlight then just a discrete single cell.210 The first tandem solar cell

was made up of small organic molecules,211 but, since then, research has expanded to

solution-processed bulk heterojunction cells with blends of MDMO-PPV:PC60BM212 and

P3HT/PCBM: ZnPc/C60.213 The largest PCE of any bulk heterojunction tandem solar cell

was reported by Kim and co-workers.214 The cell is entirely solution processed with the

top cell comprised of a P3HT:PC70BM:PEDOT/PSS blend while the bottom cell was a

PCPDTBT: PCBM:PEDOT/PSS blend. The cells were separated by a titanium dioxide

layer. This cell had a 38% performance increase and a PCE of an unprecedented 6.5%.

5.5 Critical Parameters for Organic Solar Cells

Many different electron-acceptors have been employed in BHJ devices. The most

widely used acceptor to date is Buckminsterfullerene C60, which can accommodate up to

six electrons in a reductive process. Due to its limited solubility, other more soluble C60

derivatives such as 1-(3-methoxycarbonyl)propyl-1-phenyl[6,6]C61 (PCBM) have been

utilized in devices.215 Derivatives of C60 make great electron acceptors in BHJ devices

because of their low lying LUMO, which makes the transfer of an electron from the p-

type material thermodynamically favorable.216 Also, electron transfer from the donor

materials to the C60 derivatives takes place in close to 45 femtoseconds, which is faster

than the donor electrons decay back to their ground state.217

71

For n-type materials, C60 derivatives are the frontrunner; however, synthesis of

new hole-type donor materials is imperative. To date, these p-type donor materials are

mostly based on conjugated polymers.

Excitement has been building in academic and commercial laboratories due to the

possibility of producing large scale BHJ solar cells that can be easily processed at low

cost with good efficiency. However, optimization of these devices is still needed in order

to compete with silicon technologies. There are some considerations needed when

determining how to build the ideal polymer solar cell device: 1.) the band-gap of the

polymer. 2.) the LUMO of the donor. 3.) the minimum offset of LUMOs between donor

and acceptor. 4.) the fill factor and open circuit voltage. 5.) how the device is assembled.

The band-gap of a polymer is the difference in energy (ΔeV) between the HOMO

and the LUMO. These can range from 1.5 eV (semi-conductor) to 3 eV (insulator) based

on the monomers chosen. A band-gap of 1.1 ev (1100 nm) can absorb about 77 % of all

solar energy photons;218-219 however, most donor polymers have band-gaps around 2 eV

(620 nm), which greatly limits these donor polymers as potential materials in

photovoltaic devices.198 Researchers are in need of new low band-gap polymers in order

to harvest solar energy reaching the earth more efficiently.

The LUMO of the donor polymer is also very important. The ideal LUMO energy

level for a donor is -3.9 eV, which can give PCEs of close to the theoretical limit of 10 %

if the polymer has a low band-gap.220-221 The minimum offset in LUMO’s between the

donor polymer and the PCBM acceptor is essential to facilitate electron transfer in order

to obtain charge separation and, in turn, a photo-current.222-223 If the LUMO energy level

of the donor is ideally around -3.9 eV, the LUMO energy level of the acceptor should be

72

a minimum of 0.3 eV lower. The LUMO energy level of PCBM is -4.2 eV, which makes

this material an ideal acceptor.

Finally, understanding how to tailor the intrinsic properties of the polymer can be

imperative to achieve high efficiencies. In order to investigate the nanomorphology of the

polymer, electron microscopy is used. Nanoscale phase separation can be seen in some

polymer solar cell devices, which can be detrimental to the device, owing to insufficient

mixing of the donor and acceptor materials. Solvents can also influence the

nanomorphology and degree of phase separation in a polymer film. Shaheen and co-

workers224 found that if an MDMO-PPV/PCBM film is spin-coated from toluene, a PCE

of 0.9 % can be achieved. When the solvent is changed to chlorobenzene, an increase in

PCE to 2.7 % is seen. This is attributed to chlorobenzene being a better solvent than

toluene. The blending of the polymer and fullerene in the film is improved in

chlorobenzene, while the polymer and fullerene tend to phase separate into large domains

in toluene, which is harmful to the device efficiencies due to the greater probability of the

exciton recombining in the larger domains. The increased PCE may also be attributed to

the slower drying time of the chlorobenzene film compared to toluene film, which will

give a more crystalline phase within the photoactive layer. The ratio of polymer to

fullerene can affect the morphology and efficiency of the solar cell device. One of the

components may overwhelm the other within the film, inducing segregation of the

materials.

Thermal annealing has also been shown to increase PCEs in P3HT/PCBM based

solar cell devices.225-226 By heat treatment of the device above the glass transition

temperature of the polymer, the film can reorganize and give a more crystalline phase.

73

This makes a P3HT device increase from 2.9 % (unannealed) to almost 6 %

(annealed).227 Understanding how to tailor the intrinsic properties of the polymer, as well

as fabricating the device properly, will allow one to reach PCEs of up to 10 % for

polymer-based solar cell devices and jumpstart polymer solar cell production to become

competitive with silicon devices.

5.6 Research Goal

The goal of this research project is to synthesize and characterize new low band

gap polymers for organic photovoltaic applications. The literature consists of hundreds of

polymers that have been fabricated into solar cell devices and tested under solar radiation.

The problem with the majority of these devices is they achieve low efficiencies (< 2 %)

due to either their low molecular weight or their insolubility and, subsequently, poor

processability. Linear alkoxybenzodithiophene/2,1,3-benzothiadiazole (BDT/BT)-based

donor-acceptor copolymers give good open circuit voltages; however, they have poor

current production, molecular weight and power conversion efficiency due to the

insolubility of the linear side chain. The goal of this research project is to synthesize and

characterize new low band gap copolymers based on BDT that are of high molecular

weight and can be solution processed. This will be accomplished by attaching a branched

2-ethylhexyl side chain to the 4- and 8- positions of the BDT unit. Branched side chains

tend to frustrate aggregation, allowing for the polymer to remain soluble in the reaction

solution in order for it to grow and achieve high molecular weights. These copolymers,

incorporating branched side chains, will allow us to obtain a chloroform-soluble fraction

with a high average molecular weight. Other highly branched systems, such as 3-octyl

74

and 6-undecyl, will be attached to the 4- and 8- positions of the BDT unit in order to

achieve good solubility and high molecular weight. The band gap, HOMO and LUMO

energy levels of the copolymer can be tuned by changing the electron-donating or

withdrawing comonomers from BDT and BT to other donors and acceptors based on

cyclopentadithiophene (CPDT) and 2,1,3-benzoselenadiazole (BSe), 1,2,5-

selenadiazolo[3,4-c]pyridine (PSe), 1,2,5-thiadiazolo [3,4-c]pyridine (PT) and 2,1,3-

benzoxadiazole (BO). The synthesis will be carried out in order to decrease the band gap

and increase absorption and current production in the devices. Once synthesized, the

polymers will be fabricated into bulk heterojunction (BHJ) solar cells and tested under

AM 1.5 g solar radiation.

75

CHAPTER 6: EXPERIMENTAL

6.1. Materials

Diethylamine, thionyl chloride, n-butyllithium (1.6M in hexanes), trimethyltin

chloride, 2-ethylhexyl bromide, undecan-6-ol, methanesulfonyl chloride, benzofurazan

and 3-octanol were obtained from Sigma-Aldrich Chemical Co (Milwaukee, WI). 3-

Thiophenecarboxylic acid and 3,4-thiophenedicarboxylic acid were obtained from Matrix

Scientific Co (Columbia, SC). Palladium tetrakistriphenylphosphine was obtained from

Acros Chemical Co (Pittsburgh, PA). 1-bromododecane and tetrabutylammonium

bromide were purchased from Eastman Chemical Co (Rochester, NY). Bromine, zinc

dust, toluene and methanol were purchased from Fisher Chemical Co (Milwaukee, WI).

4H-Cyclopenta-[1,2-b:5,4-b’]dithiophene was purchased from Astar Pharma (Allison

Park, PA). 2,1,3-Benzoxadiazole was purchased from Maybridge Chemical Co (Cornwall,

England, UK). Glassy carbon (d = 1.5 mm or 2 mm) mini-electrodes were purchased

from Cypress Systems (Fresno, CA).

6.2. Methods

6.2.1. Analytical Methods

1H and 13C-NMR spectra were recorded on a Bruker Avance DPX-300 NMR

sprectrometer. 119Sn NMR spectra were recorded on a Bruker Avance DRX-500 NMR

spectrometer. UV-visible absorption spectra were recorded on an Agilent 8453 diode-

array spectrophotometer operating over a range of 190-1100 nm. Flash chromatography

was performed on a Biotage IsoleraTM Flash Purification System using Biotage SNAP

76

Flash Purification Cartridges as the stationary phase. DSC was performed at 20oC/min

from 0oC to 250oC under nitrogen gas (50 mL/min) using a TA Instruments DSC Q200.

Microwave-assisted polymerizations were carried out using a CEM Discover Microwave

reactor. Gel permeation chromatography (135°C in 1,2,4-trichlorobenzene) was

performed by American Polymer Standards (Ohio).

6.2.2. Electrochemical Methods

Electrochemical measurements were carried out using a computer-controlled Pine

Model AFCBP 1 Bi-Potentiostat with PineChem software in a standard single-

compartment, three electrode cell. The working electrode was glassy carbon; the counter

electrode was a Pt flag. A silver wire was used as a pseudo-reference electrode and was

periodically calibrated against the Fc/Fc+ couple. All measurements were carried out in

degassed solutions under dry nitrogen. Freshly distilled acetonitrile was used as the

solvent and the supporting electrolyte was electrochemical grade tetrabutylammonium

hexafluorophosphate (0.1 M). The scan rate in all cases was 100 mV/s. The

electrochemical onsets were determined as the position where the current differed by 2

µA from the baseline. The highest occupied molecular orbital (HOMO) and lowest

unoccupied molecular orbital (LUMO) energy levels were calculated from the oxidation

and reduction onsets respectively according to a published equation.228

6.2.3. X-Ray Diffraction Methods

Powder diffraction data were collected at room temperature using instruments and

procedures as discussed in the X-ray diffraction methods section of Chapter 2.

77

6.2.4. Photovoltaic Methods

The following experiments were conducted by Eric D. Peterson, Wanyi Nie, and

Gregory Smith of the Wake Forest University Dept. of Physics and the Wake Forest

University Center for Nanotechnology and Molecular Materials.

A general procedure for fabrication of a solar cell device. ITO-coated glass slides

(Delta Technologies) were cleaned by sonication in acetone and isopropanol for 20

minutes each, followed by ozone cleaning for 30 minutes. A solution of PEDOT:PSS

(Clevios P – H.C. Starck) at 1:1 PEDOT:PSS solution to deionized water was spin coated

onto the slides at 4000 RPM (resulting in a 40 nm layer). The films were then baked in a

vacuum oven at 100 C for 30 minutes. Polymer solutions were then spin coated onto the

PEDOT:PSS coated substrates. Solutions were prepared by mixing polymer and 1,2-

dichlorobenzene (8 mg/mL-10 mg/mL), then they were heated (80 °C - 100 °C) and

stirred for 24 hr. The solutions were then filtered while hot (0.45 µm PVDF (Millipore)),

and spin coated at 1500 RPM for 40 s. The films were set to dry for 30 minutes and then

placed under vacuum for thermal deposition of electrodes (2 nm LiF/100 nm Aluminum).

The active area of the device is 38 mm2. All film thicknesses and surface profiles were

determined via a JEOL JSPM-5200 operating in AFM tapping mode. The current-voltage

(J-V) characteristics were measured with a Keithley 260 digital source meter under

simulated air mass (AM) 1.5 solar irradiation of 100 mW/cm2 (Oriel 150W Xenon Light

Source). The light intensity was calibrated with a NREL calibrated reference cell

(Newport). The external quantum efficiency (EQE) curve was measured using a 300 W

Oriel Xenon light source passed through an Oriel Cornerstone 260 monochramotor, a

78

Merlin lock-in amplifier, a calibrated Si UV detector, and a SR 570 low noise current

amplifier.

6.3. Synthesis

4,7-Dibromo-2,1,3-benzothiadiazole (21),229 4,7-dibromo-2,1,3-pyridinethia-

diazole (22),230 4,7-dibromo-2,1,3-benzoselenaadiazole (23),231 4,7-dibromo-2,1,3-

pyridine-selenaadiazole (24),231 and 4,7-dibromo-2,1,3-benzoxadiazole (25)232 were

synthesized according to literature procedures. The non-stannylated 4,8-

didodecyloxybenzo[1,2-b:4,5-b’]dithiophene (29) and 4,8-bis(2-ethylhexyloxy)benzo

[1,2-b:4,5-b’]dithiophene (30) were synthesized according to the published

procedures.233-234 4,4-Bis(2-ethylhexyl)-2,6-bis(trimethylstannyl)-4H-cyclopenta-[2,1-

b;3,4-b’]dithiophene (33) and 1,3-dibromo-5-octylthieno[3,4-b]pyrrole-4,6-dione (38a)

and 1,3-dibromo-5-(2-ethylhexyl)thieno[3,4-b]pyrrole-4,6-dione (38b) were synthesized

according to the published procedures.235-237

Undecan-6-yl methanesulfonate (26). To a dry 500 mL round-bottom flask containing

250 mL of dichloromethane was added undecan-6-ol (30.0 g, 0.174 mol), and methane-

sulfonylchloride (14.0 mL, 0.181 mol). Triethylamine (26.0 mL, 0.186 mol) was then

added dropwise to the solution via syringe. After stirring for one hour at room

temperature, the solvent was removed in vacuo, and the oily residue was extracted with

diethyl ether (500 mL) and washed with 3 x 250 mL of water. The organic layer was

dried over anhydrous MgSO4, filtered and evaporated. The yellow/brown oil was purified

by flash chromatography (9:1 hexane:dichloromethane) to give the title compound. Yield

(31.6 g, 72.5 %). 1H-NMR (CDCl3), δ (ppm): 4.69 (quintet, 1H), 2.99 (s, 3H), 1.74 – 1.63

79

(m, 4H), 1.45-1.22 (m, 12H), 0.893 ppm (t, 6H). 13C-NMR (CDCl3), δ (ppm): 84.36,

39.26, 35.05, 32.23, 25.38, 23.26, 14.85 ppm.

N,N-Diethylthiophene-3-carboxamide (27). 3-Thiophenecarbonyl chloride (13.2 g,

0.09 mol) was dissolved in methylene chloride (45 mL) and added drop-wise at 0oC to a

solution of diethylamine (25 mL) in methylene chloride (25 mL). The solution was stirred

at 0oC for 2 hours and then at RT overnight. Diethylamine (10 mL) was added and

mixture was stirred for another 2 hours. The diethylamine hydrochloride precipitate was

filtered off and the organic phase was extracted with water. The solution was dried over

magnesium sulfate and evaporated to give a brown oil. (14.1 g, 85%). Characterization of

the product is consistent with the published data.122 One pot procedure. 3-

Thiophenecarboxylic acid (7.0 g, 0.055 mol) and thionyl chloride (5.0 mL, 0.068 mol)

were added to a round bottom flask containing methylene chloride (200 mL) and this was

cooled to 0 °C. Triethylamine (15 mL) was then added drop-wise over 15 minutes

resulting in the formation of a white precipitate. The mixture was allowed to warm to

room temperature. After 30 minutes diethylamine (8 mL) was added drop-wise over 10

minutes. The mixture was stirred for additional 30 minutes at room temperature. The

methylene chloride was evaporated, then ether was added and the triethylamine

hydrochloride precipitate was filtered and washed with a small amount of ether. The ether

was then evaporated to leave a brown oil (8.6 g, 86 %). Characterization of the product

was consistent with the published data.233

4,8-Dihydrobenzo[1,2-b;4,5-b’]dithiophene-4,8-dione (28). Compound 27 (14.1 g,

0.077 mol) was added to a 2-neck round bottom flask that was charged with dry THF (50

mL). 1.6M n-Butyllithium in hexanes (51 mL, 0.082 mmol) was added drop-wise over 30

80

minutes at 0oC. The mixture was allowed to stir at 0oC for 30 minutes and then at RT for

2 hours. The mixture was poured over ice and allowed to stand for 4 hours. The

precipitate was filtered and washed with water and methanol and dried in air overnight.

Typical yields range from 75-92 %. Characterization of the product was consistent with

the published data.233

4,8-Bis(1-ethylhexyloxy)benzo[1,2-b:4,5-b’]dithiophene (31). Compound 28 (4.0 g,

18.1 mmol) was added to a flask containing Zn dust (2.6 g, 39.8 mmol) and NaOH (85.0

mL, 25 %) solution. The green mixture was allowed to reflux for 1 hr. The color changed

to orange and 3-octylmethanesulfonate (7.3 g, 35 mmol) and tetrabutylammonium

bromide (600 mg, ~10 mol %) were added. After 2 hours additional portions of 3-

octylmesylate (1.34 g, 6.4 mmol) and Zn dust (1.2 g, 18.3 mmol) were added and the

mixture was refluxed overnight. After cooling, the mixture was quenched with H2O and

separated with ether. The organic phase was dried over MgSO4 and evacuated to yield an

orange oil. (4.40 g, 54%). 1H-NMR (CDCl3), δ (ppm): 7.47 (d, 2H); 7.33 (d, 2H); 4.52 (m,

2H); 1.73 (m, 8H); 1.51 (m, 4H); 1.30 (m, 8H) 1.03 (m, 6H); 0.89 (m, 6H). 13C-NMR

(CDCl3), δ (ppm): 143.1, 132.4, 130.5, 125.5, 120.7, 83.7, 33.7, 32.1, 26.9, 25.1, 22.6,

14.0, 9.6. MS (EI): calc’d 446.23, found (M+1)+, 447.3.

4,8-Bis(undecan-6-yloxy)benzo[1,2-b:4,5-b’]dithiophene (32). Compound 28 (4.4 g,

20 mmol) was added to a flask containing zinc powder (3.4 g, 52 mmol),

tetrabutylammonium bromide (2.0 g, 6.2 mmol) and 60 mL of 25% NaOH solution. The

reaction was stirred and heated to reflux for 1 hr, and then 6-undecanylmethanesulfonate

(15.0 g, 60 mmol) was added. The reaction was stirred for 2 hr at reflux, giving an orange

suspension. An additional amount of Zn powder (1.2 g, 20 mmol) was added to ensure

81

completion of the reaction, and the mixture was refluxed overnight (~16 hr). The reaction

mixture was poured into water and extracted with ethyl ether, dried over MgSO4, filtered

and evaporated to give a yellow oil (8.6 g, 81 %). Analysis of this material by GC/MS

showed a 95:5 mixture of the product (M/Z = 530), and an impurity (M/Z = 514). The

impurity can be removed via flash chromatography (pure hexanes ramping to 8:2

hexanes:dichloromethane), resulting in 5.5 g (52 %) of pure 32. 1H-NMR (CDCl3), δ

(ppm): 7.44 (d, 2H), 7.30 (d, 2H), 4.56 (quintet, 2H), 1.75-1.60 (m, 8H), 1.55 – 1.38 (m,

8H), 1.38-1.15 (m, 16H), 0.89 ppm (t, 12H). 13C-NMR (CDCl3), δ (ppm): 143.11, 132.42,

130.44, 125.51, 120.73, 82.57, 34.31, 32.09, 25.07, 22.64, 14.05 ppm.

General procedure for stannylation of compounds (34), (35), (36) and (37).

Compounds 29-32 in dry THF (20 equiv. by wt.) were cooled to -78oC in an acetone/dry

ice bath. n-Butyllithium (2.2 equiv, 1.6 M) in hexanes was added dropwise. The solution

was stirred at -78 °C for 30 minutes and then at RT for 2 hours. The solution was then

cooled to -78 °C and freshly prepared trimethyltin chloride solution (2.4 equiv, 20% by

wt. in THF) was added dropwise and the solution was allowed to stir at RT overnight.

The solution was poured into water and extracted with ethyl ether. The solution was

washed with water and the organic phase was dried over anhydrous MgSO4 and

evacuated to give a waxy yellow solid (> 95 % yield). White powders could be obtained

by triturating with EtOH. No difference in purity was observed via NMR spectroscopy,

nor were there differences observed in subsequent polymerization reactions.

2,6-Bis(trimethyltin)-4,8-(1-dodecyl-oxy)benzo[1,2-b:4,5-b’]dithiophene (34). Yield;

64 % 1H-NMR (CDCl3), δ (ppm): 7.52 (s, 2H); 4.30 (t, 4H); 1.89 (m, 4H); 1.59 (m, 4H);

1.23-1.43 (m, 32H); 0.89 (t, 6H); 0.46 (s, 18H). 13C-NMR (CDCl3), δ (ppm): 143.2,

82

140.5, 134.5, 133.0, 128.0, 73.6, 32.0, 30.6, 29.8, 29.7, 29.5, 29.4, 26.2, 22.7, 14.2, -8.3.

119Sn-NMR (CDCl3), δ (ppm) relative to SnMe3Cl (164), -33.99.

2,6-Bis(trimethyltin)-4,8-bis(2-ethylhexyl-oxy)benzo[1,2-b:4,5-b’]dithiophene (35).

Yield; 73 %. 1H-NMR (CDCl3), δ (ppm): 7.53 (s, 2H); 4.20 (d, 4H); 1.54-1.64 (m, 4H);

1.33-1.88 (m, 18H); 1.04 (t, 6H) 0.96 (t, 6H) 0.46 (s, 18H). 13C-NMR (CDCl3), δ (ppm):

143.3, 140.4, 133.9, 132.9, 128.0, 75.7, 40.7, 30.6, 29.3, 24.0, 23.2, 14.2, 11.4, -8.3.

119Sn-NMR (CDCl3), δ (ppm) relative to SnMe3Cl (164), -33.91.

2,6-Bis(trimethyltin)-4,8-bis(1-ethylhexyl-oxy)benzo[1,2-b:4,5-b’]dithiophene (36).

Yield; 87 %. 1H-NMR (CDCl3), δ (ppm): 7.53 (s, 2H); 4.58 (m, 2H); 1.74 (m, 8H); 1.56

(m, 6H); 1.33 (m, 8H); 1.05 (m, 6H) 0.90 (m, 6H) 0.44 (s, 18H). 13C-NMR (CDCl3), δ

(ppm): 141.8, 139.8, 134.4, 133.8, 128.7, 83.2, 33.7, 32.2, 27.0, 25.1, 22.7, 14.1, 9.7, -

8.3. 119Sn-NMR (CDCl3), δ (ppm) relative to SnMe3Cl (164), -34.18.

2,6-Bis(trimethylstannyl)-4,8-bis(1-pentylhexyl-oxy)benzo[1,2-b:4,5-b’]dithiophene

(37). Yield; 84 %. 1H-NMR (CDCl3), δ (ppm): 7.49 (m, 2H), 4.61 (quintet, 2H), 1.75-

1.62 (m, 8H), 1.55 – 1.41 (m, 8H), 1.37-1.15 (m, 16H), 0.89 (t, 12H), 0.43 ppm (m, 18H).

13C-NMR (75 MHz, CDCl3): δ = 141.27, 139.21, 133.87, 133.27, 128.17, 82.34, 35.03,

32.96, 25.94, 23.62, 15.11, -7.08 ppm. 119Sn NMR (CDCl3): δ (ppm) relative to SnMe3Cl

(164), -34.30.

General procedure for polymer synthesis of P1-P14. Under ambient atmosphere in a

5 mL microwave tube equipped with a stir bar was added the bis(trimethyltin) monomer

(0.5 mmol) along with the dibromo monomer (0.485 mmol) and 2 mL of chlorobenzene.

The tube was stirred for 5 minutes and tetrakis(triphenylphosphine)palladium(0) (2.5-5

mol %) was added and the tube was capped and set in the microwave at 200 °C for 10

83

minutes. The viscous gel was precipitated in methanol and filtered. The solid was then

added to a Soxhlet thimble and subject to extractions with hexanes (6 hrs), THF (24 hrs)

and finally chloroform (24 hrs). The chloroform extract was evaporated almost to

completion and methanol was added to precipitate the polymer, which was filtered and

dried under vacuum for 24 hours.

poly[(4,8-bis(1-dodecyl-oxy)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-2,1,3-

benzothiadiazole-4,7-diyl] (P1). (Yield from CHCl3 extract, 5-30%). FT-IR (cm-1): 2917

(s), 2849 (s), 1577 (m), 1524 (m), 1489 (m), 1450 (s), 1400 (m), 1354 (s), 1273(m), 1177

(s), 1038 (br), 908 (m), 854 (m), 816 (s), 750 (w), 718 (m), 689 (m). GPC (TCB, 135oC):

Mn = 4,760 g/mol, Mw = 6,310 g/mol, PDI = 1.33. λmax (1,2-dichlorobenzene): 598 nm.

poly[(4,8-bis(2-ethylhexyl-oxy)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-2,1,3-

benzothiadiazole-4,7-diyl] (P2). (Yield from CHCl3 extract, 5-20%). FT-IR (cm-1): 2951

(m), 2916 (s), 2850 (s), 1573 (m), 1523 (m), 1487 (m), 1447 (s), 1397 (m), 1351 (s),

1257(w), 1175 (s), 1030 (br), 906 (m), 852 (w), 817 (s), 715 (w), 688 (w). GPC (TCB,

135oC): Mn = 2,880 g/mol, Mw = 3,430 g/mol, PDI = 1.19. λmax (1,2-dichlorobenzene):

579 nm.


benzothiadiazole-4,7-diyl] (P3). (Yield from CHCl3 extract, 56%). FT-IR (cm-1): 2951

(m), 2916 (s), 2852 (s), 1575 (m), 1523 (m), 1486 (m), 1448 (s), 1396 (m), 1337 (s),

1257(w), 1178 (s), 1019 (br), 906 (m), 853 (w), 818 (s), 715 (w), 688 (w). GPC (TCB,

135oC): Mn = 27,100 g/mol, Mw = 68,800 g/mol, PDI = 2.54. λmax (1,2-dichlorobenzene):

637 nm.

84


pyridinethiadiazole-4,7-diyl] (P4). (Yield from CHCl3 extract, 20 %). FT-IR (cm-1): 2940

(m), 2924 (s), 2854 (m), 1547 (s), 1522 (m), 1439 (s), 1433 (s), 1339 (m), 1301 (m), 1178

(m), 1110 (m), 1072 (m), 1020 (s), 914 (m), 847 (m), 767 (m). λmax (CHCl3): 665 nm.


benzoselenadiazole-4,7-diyl] (P5). (Yield from CHCl3 extract, 52 %). FT-IR (cm-1): 2945

(m), 2920 (s), 2853 (s), 1562 (m), 1521 (m), 1455 (m), 1438 (s), 1396 (m), 1338 (s), 1287

(w), 1114 (s), 1019 (br), 9010 (m), 852 (w), 827 (s), 719 (w). λmax (CHCl3): 659 nm.


pyridineselenadiazole-4,7-diyl] (P6). (Yield from CHCl3 extract, 31 %). FT-IR (cm-1):

2940 (m), 2924 (s), 2854 (m), 1547 (s), 1522 (m), 1439 (s), 1433 (s), 1339 (m), 1301 (m),

1178 (m), 1110 (m), 1072 (m), 1020 (s), 914 (m), 847 (m), 767 (m). λmax (CHCl3): 736

nm.

poly[4,8-bis(1-pentylhexyl-oxy)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-2,1,3-

benzothiadiazole-4,7-diyl] (P7). (Yield from CHCl3 extract, 70 %). FT-IR (cm-1): 2945

(m), 2925 (s), 2854 (m), 1578 (s), 1523 (m), 1487 (m), 1444 (s), 1339 (m), 1254 (m),

1179 (m), 1118 (m), 1019 (s), 908 (m), 833 (m), 817 (s), 720 (m). GPC: Mn = 31.2

kg/mol, PDI = 2.57. λmax (chlorobenzene): 639 nm.


pyridinethiadiazole-4,7-diyl] (P8). (Yield from CHCl3 extract, 34 %). FT-IR (cm-1): 2938

(m), 2927 (s), 2850 (m), 1549 (s), 1521 (m), 1438 (s), 1440 (s), 1338 (m), 1307 (m), 1172

(m), 1108 (m), 1072 (m), 1021 (s), 916 (m), 844 (m), 768 (m). λmax (chlorobenzene): 694

nm.

85


benzoselendadiazole-4,7-diyl] (P9). (Yield from CHCl3 extract, 63 %). FT-IR (cm-1):

2945 (m), 2920 (s), 2853 (s), 1562 (m), 1521 (m), 1455 (m), 1438 (s), 1396 (m), 1338 (s),

1287 (w), 1114 (s), 1019 (br), 9010 (m), 852 (w), 827 (s), 719 (w). λmax (chlorobenzene):

678 nm.

Poly[4,8-bis(1-pentylhexyl-oxy)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-2,1,3-

pyridineselenadiazole-4,7-diyl] (P10). (Yield from CHCl3 extract, 21 %). FT-IR (cm-1):

2945 (m), 2922 (s), 2857 (m), 1549 (s), 1520 (m), 1439 (s), 1431 (s), 1338 (m), 1302 (m),

1179 (m), 1110 (m), 1075 (m), 1022 (s), 910 (m), 843 (m), 767 (m). λmax (chlorobenzene):

741 nm.

Poly[4,8-bis(1-pentylhexyl-oxy)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-2,1,3-

benzoxadiazole-4,7-diyl] (P11). (Yield from CHCl3 extract, 51 %). FT-IR (cm-1): 2945

(m), 2925 (s), 2855 (m), 1596 (m), 1537 (s), 1449 (s), 1375 (m), 1340 (m), 1260 (m),

1182 (m), 1116 (m), 1026 (s), 1009 (s), 924 (m), 891 (m), 825 (s), 799 (m), 723 (m).

GPC: Mn = 47.2 kg/mol, PDI = 3.81. λmax (chlorobenzene): 653 nm.

poly[(4,8-bis(2-ethylhexyl-oxy)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-(5-

octylthieno[3,4-b]pyrrole-4,6-dione)-1,3-diyl] (P12). Characterization of the polymer is

consistent with the literature procedures.238-240 Yield (from CHCl3 extract, 56%). λmax

(CHCl3): known, 627 nm; found, 634 nm.

poly[(4,4-bis(2-ethylhexyl)cyclopenta-[2,1-b:3,4-b’]dithiophene)-2,6-diyl-alt-(5-

octylthieno[3,4-b]pyrrole-4,6-dione)-1,3-diyl] (P13). Yield (from CHCl3 extract, 49 %).

1H-NMR (500 MHz, CDCl3), δ (ppm): 7.98 (m, 2H); 3.70 (t, 2H); 2.03 (br, 4H); 1.72 (br,

2H); 1.61 (br, 4H); 1.40-1.30 (br, 12H); 1.10-0.93 (br, 15H) 0.90 (m, 4H) 0.77 (br, 9H);

86

0.67 (br, 6H). 13C-NMR (125 MHz, CDCl3), δ (ppm): 162.67, 160.57, 140.30, 136.33,

134.08, 128.00, 54.52, 43.03, 38.70, 35.42, 34.25, 31.84, 29.29, 29.22, 28.66, 28.58,

27.57, 27.06, 22.89, 22.67, 14.12, 14.09, 10.76. FT-IR (cm-1): 2917 (s), 2853 (s), 1736

(m), 1697 (s), 1533 (s), 1456 (m), 1427 (m), 1379 (s), 1186 (m), 1072 (m), 1042 (s), 750

(s). GPC: Mn = 10,300, Mw = 12,800, PDI = 1.24. λmax (CHCl3): 653 nm.

poly[(4,4-bis(2-ethylhexyl)cyclopenta-[2,1-b:3,4-b’]dithiophene)-2,6-diyl-alt-(5-

ethylhexyl[3,4-b]pyrrole-4,6-dione)-1,3-diyl] (P14). Yield (from CHCl3 extract, 32 %).

1H-NMR (500 MHz, CDCl3), δ (ppm): 7.99 (m, 2H); 3.64 (br, 2H); 2.03-1.98 (br, 4H);

1.98-1.90 (br, 2H) 1.61-1.55 (br, 1H); 1.60-1.30 (br, 6H); 1.15-0.95 (br, 18H); 0.85-0.60

(br, 18H). 13C-NMR (125 MHz, CDCl3), δ (ppm): 162.96, 160.51, 140.35, 136.28, 134.10,

127.95, 54.51, 47.77, 35.92, 35.12, 34.31, 29.65, 28.60, 28.53, 27.59, 23.93, 23.14, 22.88,

14.57, 13.67, 13.43, 10.71. FT-IR (cm-1): 2953 (m), 2920 (s), 2854 (s), 1737 (m), 1697

(s), 1534 (s), 1456 (m), 1427 (m), 1377 (s), 1321 (m), 1186 (m), 1065 (s), 1011 (m), 750

(s). λmax (CHCl3): 652 nm.

87

CHAPTER 7

SYNTHESIS, CHARACTERIZATION AND

PHOTOVOLTAIC PROPERTIES OF POLYMERS P1-P3

Christopher M. MacNeill, Robert C. Coffin, Eric Peterson, Gregory L. Smith, Ronald E.

Noftle and David L. Carroll

The following chapter was accepted as a manuscript to the Journal of Nanotechnology,

2011. All of the research presented was conducted by Christopher M. MacNeill with help

from Robert C. Coffin. The photovoltaic device data was completed by Eric Peterson and

Gregory Smith. The manuscript was prepared by Christopher M. MacNeill and Robert C.

Coffin and edited by David L. Carroll and Ronald E. Noftle

88

S

O

OH

S

O

N(CH2CH3)2

HN(CH2CH3)2S

S

O

O

SOCl2

RT, 24hr

CH2Cl2

n-BuLi

THF0oC, 1hr

TEA

27 28

S

S

O

O

1. Zn dust20% NaOH

2. R-Br or R-OMsTBAB

ref lux, 24hr

1. n-BuLi

2. Sn(CH3)3Cl

THF, -78oC

RT, 24hrS

S

OR

OR

S

S

OR

OR

(H3C)3Sn Sn(CH3)3

R = 1-dodcecyl = 342-ethylhexyl = 351-ethylhexyl = 366-undecyl = 37

28 29-32

7.1. Synthesis of Polymers P1-P3

The synthetic routes to the electron-donor monomers are shown in Schemes 6 and

7. For the amounts of starting materials used in the following syntheses, see Chapter 6.

Starting from 3-thiophenecarboxylic acid, we developed a new one-pot procedure for

accessing the synthetic intermediate N,N-diethylthiophene-3-carboxamide (27).

Scheme 6: The synthesis of 4,8-dihydrobenzo[1,2-b;4,5-b’]dithiophene-4,8-dione 28.

3-Thiophenecarboxylic acid is allowed to react with one equivalent of thionyl

chloride and excess triethylamine in dichloromethane. After 30 minutes of stirring, one

equivalent of diethylamine was added to the reaction mixture containing 3-

thiophenecarbonyl chloride to form the desired product. The HCl generated by this

reaction reacts with the remaining triethylamine to form a triethylamine hydrochloride

salt which precipitates from the reaction and drives it forward.

Scheme 7: The synthesis of the bis-stannylated monomers 34-37.

89

NS

N

Br Br

N NS

S

S

O

O

n+

S

S

O

O

Sn(CH3)3(H3C)3SnPd(PPh3)4

chlorobenzene

200oC, 10 min

P2

S

S

OC12H25

OC12H25

Sn(CH3)3(H3C)3Sn

S

S

O

O

Sn(CH3)3(H3C)3Sn

microwave

P3

P1

N NS

S

S

O

O

n

N NS

S

S

OC12H25

OC12H25

n

34

35

36

21

N,N-Diethylthiophene-3-carboxamide (27) is then allowed to react with one equivalent of

n-butyllithium at 0oC to give 4,8-dihydrobenzo[1,2-b;4,5-b’]dithiophene-4,8-dione (28)

(Scheme 6). Reaction of compound (28) with zinc metal in sodium hydroxide solution

reduced the dione to the corresponding diol and deprotonated it, giving the alkoxy

species, which reacts with either an alkyl bromide or alkyl mesylate to give the 4,8-

dialkoxybenzodithiophene compounds (29-32). Reactions of compounds (29-32) with n-

butyllithium and quenching with trimethyltin chloride solution gave the bis-stannylated

monomers (34-37) (Scheme 7). Compounds 29-32 and 34-37 were prepared using

procedures similar to those in the literature.233-234

Scheme 8: The synthesis of polymers P1-P3.

90

The purity of monomers 34-37 was confirmed by 119Sn-NMR spectroscopy (Appendix

B8-B11), which is a very useful technique for determining whether any trace

monostannane impurities exist in the monomers. These impurities are detrimental to the

polymerization reactions because they can interfere with the polymers step-growth

mechanism.

Polymers P1-P3 were prepared by microwave-assisted Stille cross-coupling

polymerization of the bis-stannylated monomers 34-36 with 4,7-dibromo-2,1,3-

benzothiadiazole (21) in chlorobenzene using tetrakis(triphenylphosphine)palladium(0)

((Ph3P)4Pd) as the catalyst (Scheme 8). Microwave heating was used because it is more

efficient than conventional heating methods, and it has also been reported to give higher

molecular weights.241-245 The polymers were precipitated by adding the mixture to

methanol. The product was collected by filtration, and transferred to a Soxhlet extractor,

where the material was washed with hexanes and extracted with chloroform. The

chloroform-soluble fraction was isolated to ensure the material was sufficiently soluble

for the preparation of OPV devices. In all cases, material remained in the extraction

thimble after chloroform extraction; however, the amount of this material was highly

variable. For P1 and P2, yields from the chloroform soluble fractions were often less

than 10 %, while for P3, yields as high as 55 % were obtained. Assuming no cross

linking of the polymer had occurred, the fact that material remained in the extraction

thimble after chloroform extraction meant that the chloroform fraction contained material

with the highest molecular weight that is soluble in chloroform. The molecular weights of

the these fractions were determined by gel permeation chromatography (GPC) at 135 °C

using 1,2,4-trichlorobenzene as the solvent and the results are summarized in Table 1.

91

40

50

60

70

80

90

100

110

50 150 250 350 450 550

Temperature (oC)

Wei

gh

t %

P1, P2 and P3 were found to have weight average molecular weights (Mw) of 6.3, 3.4 and

68.8 kg/mol respectively.

7.2. Thermogravimetric Analysis of P1-P3

Thermogravimetric analysis was performed on polymers P1-P3 under argon at

5 °C/min as shown in Figure 25. The results indicate that the polymers have similar

thermal stabilities with the onsets of degradation ranging from 268 and 278 °C. This

degradation has been attributed to the loss of the alkoxy side chains from the BDT unit

(P1; calc., 53.3 %; found, 48.5 %: P2-P3; calc., 44.3 %; found, 38.8 %), which is

supported by the fact that P1, which has a twelve carbon side chain, loses a larger weight

percentage compared with P2 and P3, which have eight carbon side chains.

Figure 25: The TGA curve of P1 (black), P2 (blue) and P3 (red) under argon at 5oC/min.

Complete loss of the polymer structure was observed above 440oC. These high

degradation temperatures make the polymer suitable for organic-based solar cell devices.

92

300 400 500 600 700 800

Wavelength (nm)

Ab

sorb

ance

(a.

u.)

7.3. UV-Vis Spectroscopy of P1-P3

UV-visible absorption spectra for polymers P1-P3 in dichlorobenzene solution

(DCB) are shown in Figure 26. P2 is considerably blue-shifted from P1, with a λmax of

579 nm compared to 598 nm for P1. This is indicative of a lower molecular weight

material which was confirmed using GPC analysis. The shape of the absorption profile

Figure 26: The UV-vis absorption spectra of P1 (black), P2 (blue) and P3 (red) in DCB.

for P3 is very different from those of P1 and P2 with a very sharp, low-energy feature

dominating the spectrum, resulting in a λmax of 637 nm. This sharp, low-energy feature

has been seen in other low band gap copolymers and is indicative of high molecular

weight and often better solar cell performance.241, 246-248

7.4. Electrochemistry of P1-P3

Cyclic voltammetry measurements were made on polymer films of P1-P3. The

films were prepared by drop-casting chloroform solutions of the polymers onto a glassy

carbon electrode (Figure 27). The onsets of the oxidation and reduction potentials for the

93

three polymers were comparable because they share a common backbone. These results

are summarized in Table 3. The oxidation onsets, determined as the point where the

current differed from the baseline by 2 µA, were found to be 0.15, 0.13 and 0.12 V for P1,

P2 and P3 giving rise to HOMO levels of -4.95, -4.93 and -4.92 eV respectively.

Figure 27: The cyclic voltammograms of P1 (black), P2 (blue) and P3 (red) films drop-

cast from chloroform solution.

Table 3: Table of results from electrochemical and UV-visible spectroscopy

measurements of polymers P1-P3.

λmax (nm)

ΔEgopt

(eV) Eox onset

(V) HOMO

(eV) Ered onset

(V) LUMO

(eV) ΔEg

elect (eV)

P1 600 1.67 0.15 -4.95 -1.72 -3.08 1.87 P2 575 1.74 0.13 -4.93 -1.62 -3.18 1.75 P3 637 1.72 0.12 -4.92 -1.59 -3.21 1.71

Similarly, the reduction onsets were found to be -1.72, -1.62 and -1.59 V for P1, P2 and

P3 giving rise to LUMO levels of -3.08, -3.18 and -3.21 eV respectively. These results

give electrochemical band-gaps of 1.87, 1.75 and 1.71 eV for P1, P2 and P3.

-2.2 -1.7 -1.2 -0.7 -0.2 0.3 0.8

Potential vs. Fc/Fc+ (V)

Cu

rre

nt

25μA

94

7.5. X-Ray Powder Diffraction of P1-P3

To give insight into the internal packing structure of the polymers, powder x-ray

diffraction (PXRD) was used. Samples were mounted on a loop and two frames were

measured at 2θ = 20 and 50° with exposure time of 180 seconds/frame. The integrated

diffraction patterns are shown in Figure 25. For the inset powder diffraction pattern, 10

frames were measured at 2θ = 25° with an exposure time of 180 seconds/frame, then they

were added together. This was necessary to detect the d2-spacing of P3. The intensities

of the diffraction patterns decrease and diffraction peak widths increase from P1 to P2 to

P3, indicating that structural order within the solid polymers decreases from P1 to P3.

However, the degree of order has been shown to be dependent on Mw, with high Mw

materials showing less order. The peaks at low angle (2θ = 4.15° for P1, 5.7° for P2 and

5.5° for P3) are assigned to the intermolecular distance between the polymer main chains

separated by an alkoxy side chain (d1-spacing, see Figure 28a). The 1-dodecyloxy chain

(P1) gives the longest d1-spacing at 21.3 Å while the shorter 2-ethylhexyloxy (P2) and 3-

octyloxy (P3) side chains give small d1-spacings (15.5 and 16.1 Å, respectively). A plot

of the low angle d-spacing vs. no. of carbon atoms for the three polymers gave a slope of

0.98 Å / carbon atom, which is indicative of an interdigitation packing mode (see Figure

28b), not an end-to-end packing mode like that seen in polythiophenes.249-251 The peak at

2θ = 8.3° for P1 corresponds to the second order peak of 2θ = 4.15°. The peaks at 2θ =

24.9° for P1, 24.5° for P2 and 23.8° for P3 correspond to the π-π stacking distances (d2-

spacings) 3.58, 3.63 and 3.74 Å for P1, P2 and P3 respectively. Despite the increase in

the π-π stacking distance due to the 3-octyl chain, it is worth noting that P3 still has a

95

smaller π-π stacking distance than poly(3-hexylthiophene);252 thus, our method of

increasing Mw is likely not detrimental to solar cell performance.

Figure 28: (a) The integrated powder diffraction patterns for P1 (black), P2 (blue) and

P3 (red). Inset: 10 frames added together for P3. (b) A model of packing for P3.

7.6. Photovoltaic Properties of P1-P3

The photovoltaic characteristics of the polymers were determined using a standard

bulk heterojunction device architecture – ITO/PEDOT:PSS/P1-P3:PC61BM/LiF/Al. The

devices (0.38 cm2) were fabricated under an inert atmosphere and tested in air. The active

layers were deposited from 1,2-dichlorobenzene solutions (8 mg/mL for P2 and P3, 10

mg/mL for P1) and the optimal weight ratios of polymer:PC61BM was determined to be

1:2.5 for P1 and P3 and 1:2.2 for P2. The active layer thickness for the optimal devices

as determined by atomic force microscopy (AFM) were 130, 50 and 100 nm for P1, P2

and P3 respectively. Due to the poor solubility of P2 and its low Mw, thicker films could

not be achieved even at the lowest spin speeds. The current-voltage (J-V) curves for the

96

best devices for each polymer are shown in Figure 29, and the results are summarized in

Table 4.

Figure 29: Current-voltage characteristics of BHJ solar cells based on P1 (black), P2

(blue) and P3 (red) with PC61BM.

The open circuit voltages (Voc) are similar for the three polymers, near 0.7 V, which is

consistent with the HOMO levels determined by cyclic voltammetry. The short circuit

current density (Jsc) for P1 and P2 are similarly low (near 1 mA/cm2), while Jsc is much

higher for P3 at 8.93 mA/cm2. The fill factors (FF) increase with increasing Mw peaking

at 0.46 for P3. Consequently, P3 has a much higher power conversion efficiency (PCE)

peaking at 2.91 % compared with 0.31 % for P1 and 0.19 % for P2.

Table 4: Photovoltaic characteristics of best devices prepared from P1-P3 and PC61BM.

Voc (V)

Jsc (mA/cm2)

FF PCE (%)

P1 0.69 1.22 0.42 0.33 P2 0.71 0.81 0.33 0.19 P3 0.73 8.93 0.46 2.99

97

The EQE spectra for the P1 and P2 devices (seen in Figure 30) show poor current

generation across the spectrum with peak EQE less than 12 %. P3, on the other hand,

shows EQE above 30 % from 330-670 nm, with a peak near 51 % at 370 nm. Between

400 and 600 nm, the EQE dips, indicating that current production could be enhanced by

using PC71BM instead of PC61BM as PC71BM absorbs in this range.253

Figure 30: External quantum efficiency spectra of BHJ solar cells based on P1 (black),

P2 (blue) and P3 (red) with PC61BM.

P3 outperforms P1 and P2 across the board, with higher Voc, Jsc, FF and PCE. It is worth

noting that the P3 solar cells were prepared from pristine DCB solution without the use

of optimization techniques such as annealing or additive processing, that could greatly

enhance the PCE.

7.7. Conclusion

We prepared and characterized two new low band gap copolymers based on BDT

and BT that employ branched side chains at the 4- and 8-positions, poly[(4,8-bis(2-

98

ethylhexyloxy)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-2,1,3-benzothiadiazole-4,7-

diyl] (P2) and poly[(4,8-bis(3-octyloxy)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-

2,1,3-benzothiadiazole-4,7-diyl] (P3) as well as the previously reported linear side chain

analog, poly[(4,8-didodecyloxy)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-2,1,3-benzo-

thiadiazole-4,7-diyl] (P1). Surprisingly, transitioning from the linear 1-dodecyl side chain

P1 to the branched 2-ethylhexyl side chain P2 results in a decrease in Mw; however, by

moving the ethyl branch in one position relative to the polymer backbone P3, we observe

a dramatic increase in Mw to 68.8 kg/mol compared with 6.3 kg/mol for P1 and 3.4

kg/mol for P2. This results in vastly different optical properties, with the appearance of a

sharp low energy feature in the UV-visible absorption spectrum of P3 that is not present

in the spectra of P1 and P2. Despite the increase in the - stacking distance due to the

3-octyl branch in P3 relative to P1 and P2, the increased Mw results in an order of

magnitude increase in the PCE of the bulk heterojunction solar cells. We observe a peak

PCE of 2.91 % for devices based on P3 and PC61BM with minimal optimization

indicating that this material has the potential to make highly efficient solar cells. By

varying the side chain, we were able to take a polymer that was present in the literature,

but had poor device characteristics and improve on them by simply changing the side

chain. Also, by changing the side chain we were able to make a high molecular weight

polymer with excellent solubility and solution processability. Using a 3-octyl side chain

may now be a way of increasing the Mw in conjugated polymers; many of which have not

reached their full potential as organic photovoltaics because of poor processability and

insufficient Mw.

99

CHAPTER 8



Christopher M. MacNeill, Robert C. Coffin, Wanyi Nie, Eric Peterson, Gregory L. Smith,

Ronald E. Noftle and David L. Carroll

Some of the results from the following chapter were accepted for publication in

Macromolecular Rapid Communications, 2011. All of the research presented was

conducted by Christopher M. MacNeill with help from Robert C. Coffin. The

photovoltaic device data was completed by Wanyi Nie, Eric Peterson and Gregory Smith.

The manuscript was prepared by Wanyi Nie and Robert C. Coffin and edited by David L.

Carroll and Ronald E. Noftle.

100

N NX

Y S

S

O

O

n

36

S

S

O

O

(H3C)3Sn Sn(CH3)3

Pd(PPh3)4

chlorobenzene

200oC, 10 minmicrowave

N

NSe

N

Br Br

NSe

N

Br Br

N

NS

N

Br Br

+

X = S, Y = N; P4X = Se, Y = C; P5X = Se, Y = N; P6

22

23

24


Monomers 22-24 were used in the synthesis of polymers P4-P6 because they have

better electron-withdrawing properties than monomer 21 and consequently the band gap

of the ensuing polymers will be lowered. With a lower band gap, the polymers can absorb

more photons further into the red region of the visible spectrum. Polymers P4-P6

(Scheme 9) were synthesized according to the same procedure outlined in Chapter 7. The

yields of chloroform extract from the polymerizations varied for the different

comonomers used. For the polymers based on the pyridine monomers (P4 and P6), the

yields were low (< 30 %), while the benzene based monomer (P5), gave good yields

(82 %). These results are due to the lower solubility of nitrogen containing rings

compared with their benzene counterparts. Since the polymers weren’t appreciably

soluble


in chloroform, a bulkier side chain on the BDT unit was necessary to ensure greater

solubility. The side chain chosen was a 6-undecyloxy side chain (Scheme 6). Unlike 2-

ethylhexyloxy (35) and 3-octyloxy (36), the 6-undecyloxy group (37) is symmetric, but

101

N NX

Y S

S

O

O

n

37

S

S

O

O

(H3C)3Sn Sn(CH3)3

Pd(PPh3)4

chlorobenzene


NS

N

Br Br

N

NSe

N

Br Br

NSe

N

Br Br

N

NS

N

Br Br

+

NO

N

Br Br

X = S, Y = C; P7X = S, Y = N; P8X = Se, Y = C; P9X = Se, Y = N; P10X = O, Y = C; P11

21

22

23

24

25

since the branch is larger and has been moved in one position on the polymer backbone

relative to the 2-ethylhexyloxy, one would expect the bulkiness of this side chain to

frustrate aggregation and enhance the solubility. This guarantees that a higher Mn

material can be obtained, which is beneficial to OPV performance; however, the bulky

side chain could prevent ordering in the solid state, which may be detrimental to device

performance. 2,6-Bis(trimethylstannyl)-4,8-bis(6-undecyloxy)benzo[1,2-b:4,5-b’]

dithiophene (37) was co-polymerized with 4,7-dibromo-2,1,3-benzothiadiazole (21) to

give polymer (P7) in good yield (70 %). The polymer was soluble at >15 mg/mL at room

temperature in chlorinated aromatic solvents and had a number average molecular weight

(Mn) of 31.2 kg/mol and a polydispersity index (PDI) of 2.57 (gel permeation

chromatography, GPC, 135 °C in 1,2,4-trichlorobenzene).


102

300 400 500 600 700 800 900 1000

Wavelength (nm)

Ab

sorb

ance

(a.

u.)

Polymers (P8-P11) were synthesized using other electron-withdrawing monomers

(22-25) with 2,6-bis(trimethylstannyl)-4,8-bis(6-undecyloxy)benzo[1,2-b:4,5-b’]

dithiophene (37) (Scheme 10). The polymer yields were similar to those for the previous

polymers bearing the 3-octyloxy side chain. The benzothiadiazole (BT) based polymer

(P7) and pyridinethiadiazole (PT) based polymer (P8) were the most soluble and gave the

highest yield (70 % and 63 %), while the benzoselenadiazole (BSe) based polymer (P9)

and pyridineselenadiazole (PSe) based polymer (P10), which contained the pyridine ring,

were the least soluble and had lower yields (34 % and 21 %). Polymer (P11) had a

moderate yield (51%) and was soluble at >10 mg/mL at room temperature in chlorinated

aromatic solvents and found to have a number average molecular weight (Mn) of 47.2

kg/mol and a polydispersity index (PDI) of 3.81.

Figure 31: The UV-Vis absorption spectra of P3 (red), P4 (black), P5 (green) and P6

(pink) in DCB.

103

50

60

70

80

90

100

110

0 100 200 300 400 500 600

Temperature (oC)

Weig

ht

%

Figure 31 shows the UV-visible absorption spectrum of P3-P6. Exchanging the

BT monomer with a better accepting BSe, PT or PSe monomer can successfully decrease

the band gap and shift the λmax further into the red region. Due to the limited solubility of

P4-P6, the polymers were not further characterized and attention was focused on P7-P11,

with the more solubilizing 6-undecyl side chain.



5 °C/min (Figure 32). The results show that the polymers have similar stability with their

onsets of degradation ranging from 250 to 270 °C. These results are consistent with the

loss of side chains from the BDT polymer backbone (calculated: 36-41 % for P7-P11,

found: 38-41 %). Complete loss of the polymer structure was observed after 375oC.

These high degradation temperatures would also render P7-P11 suitable for use in

polymer solar cell devices.

Figure 32: The TGA curve of P7 (black), P8 (blue), P9 (orange), P10 (green) and P11

(red) under argon at 5oC/min.

104

8.3. UV-Visible Spectroscopy of P7-P11

UV-visible absorption spectra for polymers P7-P11 in dichlorobenzene solution

(DCB) can be seen in Figure 33. P11 is slightly red-shifted from P7, due to the oxygen

atom on the oxadiazole acceptor being more electronegative than the sulfur atom on the

thiadiazole acceptor, which gives a slightly deeper LUMO and lowers the band gap.

Similar results can be seen with other BDT and 2,7-carbazole-based copolymers.242,254

The λmax of P11 is 653 nm compared to 639 nm for P7. P9 is further red-shifted from P7

and has a λmax of 678 nm, owing to the selenium atom replacing the sulfur atom. The

larger selenium atom causes the N-Se-N bond and the C-N double bond of the

selenadiazole group to be more strained giving rise to a lower band gap and a subsequent

red shift.255-259 P8 and P10 are further red-shifted from P9 due to the nitrogen in the ring

of the pyridinethiadiazole and the pyridineselenadiazole. The nitrogen atom makes the

acceptor even more electron poor and gives rise to a lower band gap.260 The λmax of P8

and P10 is 694 and 741 nm, respectively. The solution optical band gaps generated from

Figure 33: The UV-vis absorption spectra of P7 (black), P8 (blue), P9 (orange), P10

(green) and P11 (red) in DCB.

105

-2.2 -1.2 -0.2 0.8

Potential vs Fc/Fc+ (V)

Cu

rren

t

the absorbance onset are 1.72, 1.59, 1.62, 1.47 and 1.68 eV. The shape of the absorption

profiles for P7-P11 are very similar to that from P3. This is again indicative of a high

molecular weight polymer.


Cyclic voltammetric measurements were made on polymer films of P7-P11. The

films were prepared by drop-casting chloroform solutions of the polymers onto a glassy

carbon electrode (Figure 34). The onset oxidation and reduction potentials for the five

polymers were comparable because they share a common backbone. These results are

summarized in Table 5.

Figure 34: The cyclic voltammograms of P7 (black), P8 (blue), P9 (orange), P10 (green)

and P11 (red) films drop-cast from chloroform solution.

50μA

106

The oxidation onsets, determined as the point where the current differed from the

baseline by 2 µA, were found to be 0.35, 0.44, 0.16, 0.31 and 0.50 V for P7, P8, P9, P10

and P11 giving rise to HOMO levels of -5.15, -5.24, -4.96, -5.11 and -5.30 eV

respectively. The reduction onsets were found to be -1.53, -1.29, -1.34, -1.10 and -1.25 V

for P7, P8, P9, P10 and P11 giving rise to LUMO levels of -3.27, -3.51, -3.46, -3.70 and

-3.55 eV respectively. These results give electrochemical band-gaps of 1.88, 1.73, 1.50,

1.41 and 1.75 eV for P7, P8, P9, P10 and P11.



λmax

(nm) ΔEg

opt (eV)

Eox onset (V)

HOMO (eV)

Ered onset (V)

LUMO (eV)

ΔEgelect

(eV) P7 639 1.72 0.41 -5.21 -1.38 -3.42 1.77 P8 694 1.59 0.46 -5.26 -1.23 -3.57 1.69 P9 678 1.62 0.11 -4.91 -1.39 -3.41 1.60 P10 741 1.47 0.34 -5.14 -1.10 -3.70 1.44 P11 653 1.68 0.52 -5.32 -1.23 -3.57 1.75


Powder x-ray diffraction was used to give insight into the internal packing

structure of the polymers. Samples were mounted on a loop and two frames were

measured at 2θ = 20 and 50° with exposure time of 180 seconds/frame. The integrated

diffraction patterns are shown in Figure 35. The intensities of the diffraction patterns

decrease and diffraction peaks broaden from P11 to P8 to P7 to P9 and P10, indicating

that structural order within the solid polymers decreases in the order P11 > P8 > P7 > P9

> P10. The peaks at low angle (2θ = 5.0° for P11, 5.35° for P8, 5.65° for P9, 5.55° for P7

107

3 8 13 18 23 28

2θ (degrees)

Inte

nsi

ty

and 5.40° for P10) are assigned to the intermolecular distance between the polymer main

chains separated by an alkoxy side chain (d1-spacing). The benzoxadiazole based

polymer P11 gave the longest d1-spacing at 17.7 Å. The PT polymer P8 and PSe polymer

P10 gave the next smallest d1-spacings at 16.5 and 16.4 Å, respectively, while both of the

BT and BSe polymer P7 and P9 gave the shortest d1-spacings (15.9 and 15.6 Å). These

values are comparable to those for 4,8-bis(2-ethylhexyloxy)BDT copolymers, since this

spacing is related to side chain length. A low intensity peak at 2θ = 23.6° corresponding

to a d2-spacing (π-stacking distance) of 3.8 Å is also observed for P11, and not for any of

the other polymers. This d2-spacing is larger than that of other BDT copolymers (d2 ~ 3.6

Å) likely owning to the bulk of the 6-undecyl side chain.

Figure 35: The powder diffraction patterns for P7 (black), P8 (blue) and P9 (orange),

P10 (green) and P11 (red).

d1

d2d1 = 16.5 Å

d1 = 17.7 Å

d1 = 15.9 Å

d1 = 15.6 Å d2 = 3.8 Å

d1 = 16.4 Å

108

The inset spectrum is a theoretical model of the potential packing diagram of the polymer

in the solid state. The polymer likely adopts an interdigitation packing mode, not an end-

to-end packing mode. This is due to the distance of d1-spacing. If the polymer existed in

an end-to-end packing mode, the d1-spacing would be > 20 Å.

8.6. Photovoltaic Properties of P7-P11

The photovoltaic characteristics of the polymers were determined using a standard

bulk heterojunction device architecture – ITO/PEDOT:PSS/P7-P11:PC71BM/LiF/Al. The

devices (0.38 cm2) were fabricated under an inert atmosphere and tested in air. The

results were an average of at least eight devices. A LiF hole-blocking layer was used

because it was found early-on in our study to improve Vocs by ~ 0.06 V. Similar Jsc’s

were observed for P8, P9 and P11. Polymers P9 and P10 showed lower Vocs (~0.67-0.75

V) compared to P7, P8 and P11 (>0.80 V). This is due to the low band gap nature of the

selenium based acceptor monomer. The LUMO levels are too deep, and the HOMO is too

large, and the subsequent decrease in the band gap gives rise to a decrease in Voc. The

lower band gap nature of the P9 and P10 polymers should have an increase in Jsc, which

wasn’t apparent in our J-V curves (Figure 36).

This, however, may be due to the decrease in crystallinity owing to the effect of

the selenium atom in the acceptor compared to the sulfur atoms, as observed in the PXRD

data (Figure 32). The FF is comparable for P7, P9 and P11 (> 0.46), but relatively low

for P8 and P10 (0.43-0.39). This may result from the ability of the pyridine nitrogen of

the acceptors to coordinate palladium during the polymer synthesis.

109

‐14

‐12

‐10

‐8

‐6

‐4

‐2

0

2

4

6

‐0.5 0 0.5 1

Voltage (V)

Current Density (mA/cm

2)

Figure 36: Current-voltage characteristics of BHJ solar cells based on P7 (black), P8

(blue), P9 (orange), P10 (green) and P11 (red) with PC71BM.

Once, the palladium is entrained in the polymer, it is difficult to remove.261 The

palladium may cause the excitons to recombine before the have a chance to reach the

PCBM acceptor. Alternatively, the material may not be crystalline enough to give good

charge carrier mobility and a low fill factor may result. The device characteristics of P7-

P11 are summarized in Table 6

The EQE spectra for the P7-P11 devices (Figure 37) show good current

generation across the spectrum with peak EQE at 50 % for P7 between 350 and 700 nm.

P8 shows an EQE at ~30 % from 330-750 nm. P9 showed 40 % EQE up to 500 nm, and

slowly the EQE dropped to 10% at 750 nm. P10 had the lowest EQE of any of the

polymers, at 25 % between 350 and 800 nm. P11 showed a similar EQE to P9 with much

better current generation between 600 and 700 nm. This explains the increase in PCE of

0.65 % from P9 to P11. P7 outperformed all of the other polymers in terms of Jsc and

PCE when spin coating out of pristine DCB.

110

0

10

20

30

40

50

60

300 400 500 600 700 800 900

Wavelength (nm)

EQ

E (

%)

Figure 37: External quantum efficiency spectra of BHJ solar cells based on P7 (black),

P8 (blue), P9 (orange), P10 (green) and P11 (red) with PC71BM.

Table 6: Photovoltaic characteristics of best devices prepared from P7-P11 and PC71BM.

Voc (V) Jsc (mA/cm2) FF PCE (%)

P7 0.80 10.23 0.49 3.87

P8 0.83 6.36 0.43 2.27

P9 0.75 7.55 0.46 2.59

P10 0.67 4.53 0.39 1.13

P11 0.92 7.02 0.52 3.25

8.7. Solvent Additive Processing of Polymer P11

Using 1,2-dichlorobenzene (DCB) as the solvent, P11:PC71BM weight ratios

were varied from 1:1 to 1:2.2. The Vocs and FF are relatively constant at ~ 0.92 V and

0.48, respectively, at P11:PC71BM ratios of 1:1.5 or greater. The Jsc peaks at ~7.3

mA/cm2 and the power conversion efficiency (PCE) peaks at an average of 3.06 % at a

ratio 1:1.5. The Voc is > 0.2 V higher for devices fabricated from P11 which is consistent

111

with a deeper HOMO level as determined by cyclic voltammetry. Using this optimal

P11:PC71BM ratio, devices were fabricated from chlorobenzene (CB). Despite and

improvement in the Vocs and FFs to ~ 0.97 V and 0.55, respectively, a precipitous drop in

Jsc to 2.64 mA/cm2 resulted in lower average PCEs of ~ 1.41 %.

To further improve device performance, additive processing with P11 was

investigated.262-263 Two such additives that have been shown to greatly improve device

performance are 1,8-diiodooctane(DIO)264 and 1-chloronapthalene (CN).265 Both

additives are high boiling and slow the film-drying process. They differ in that DIO has

been shown to promote polymer aggregation, which increases the domain sizes within the

film, while CN prevents polymer aggregation and decreases phase separation. Given

P11’s high solubility and poor tendency to aggregate, DIO was initially investigated as an

additive in both CB and DCB. However, DIO processing led to poorly reproducible

device performance. The effects of CN depended greatly on the host solvent.

A comparison of the PV characteristics of devices prepared from pristine CB and

DCB with those prepared with CN additive are shown in Figures 38a and b, while the

best J-V and EQE curves for each condition are shown in Figures 38c and d. Using DCB

as the host solvent, devices were fabricated from solutions containing 1 % and 2 % CN.

Both loadings resulted in a decrease in average device PCE from 3.06 % without additive

to 2.42 % with 1 % CN and 1.82 % with 2 % CN. When CB is used as the host solvent

the effect of the additives is quite different. Average PCE for devices prepared from CB

solution without additive was 1.41 %.

112

Figure 38: Summary of chlorobenzene ratio on device performance. (a) Summary of

open circuit voltage and short circuit current density. (b) Summary of fill factor and

power conversion efficiency. Points represent the average of at least eight devices with

standard deviation. (c) The best current-voltage curves, and (d) the best external quantum

efficiency curves for each condition. This figure is reproduced with permission from

Wanyi Nie.

The addition of 1, 2 and 4 % CN results in average PCEs of 2.82, 5.65, and

4.01 % respectively (Appendix B12). The best device fabricated using 2 % CN in CB

showed a Voc of 0.887 V, Jsc of 13.6 mA/cm2, FF of 0.508, and PCE of 6.05 %. The

improvements in PCEs upon addition of CN to CB are a result of dramatically improved

Jsc from an average of 2.64 mA/cm2 for pristine CB to an average of 12.43 mA/cm2 for

113

CB with 2 % CN. For both host solvents, the Voc and FF drop upon addition of the CN. A

loss in Voc is not uncommon with additive processing, presumably a result of increased

ordering stabilizing the HOMO level of the polymer. However, increases in Jsc are

typically accompanied by increases in FF, which is a result of improvements in active

layer morphology that allow for improved charge separation and collection. The external

quantum efficiency for the best device fabricated from CB with 2 % CN is above 55 %

from 350 to 670 nm reaching a maximum of 69 % at 590 nm.

8.8. Conclusion

In summary, the synthesis and characterization of polymers P4-P11 as well as the

device performance of polymers P7-P11 has been carried out. For polymers P4-P6, the

yields were relatively low because the 3-octyl side chain is not bulky enough to decrease

crystallinity and solubilize the polymers. After addition of a bulky 6-undecyl side chain,

aggregation was prevented, enabling the production of high molecular weight, freely

soluble copolymers P7-P11. UV-visible spectroscopy showed a decrease in band gap as

the electron-withdrawing nature of the acceptor increased. HOMO and LUMO levels

were calculated using cyclic voltammetry for P7-P11 and indicated that the selenium

based acceptors vastly decrease the band gap compared to the sulfur and oxygen-based

acceptors. OPV devices were fabricated for polymers P7-P11. Vocs were low for the

selenium-based acceptor polymers P9-P10 compared to P7, P8 and P11, which is normal

for lower band gap materials. The fill factor for the pyridine-based acceptor polymers P8

and P10 were lower than the benzene-based acceptor polymers P7, P9 and P11. Two

possible explanations are poor packing of the bulky 6-undecyl side chain or palladium

114

contamination due to the pyridine nitrogen atoms ability to coordinate palladium. At an

optimized P11:PC71BM ratio, solvent additive processing was employed to further

improve device performance. Using DCB as the host solvent, the addition of CN resulted

in a decrease in PCE relative to devices prepared from pristine solvent. Conversely,

devices prepared from a solution of 2% CN in CB resulted in a dramatic improvement in

PCE to an average of 5.65 %, compared with 1.41 % from pristine chlorobenzene. The

optimized devices have high Voc, but a FF around ~0.5 limits the overall PCE of these

devices.

115

CHAPTER 9



Christopher M. MacNeill, Robert C. Coffin, Eric Peterson, Ronald E. Noftle and David

L. Carroll

Some of the results from the following chapter were published as a manuscript in the

journal, Synthetic Metals, 2011 DOI: 10.1016/j.synthmet.2011.02.010. Stylistic

variations are due to the requirements of the journal. All of the research presented was

conducted by Christopher M. MacNeill with help from Robert C. Coffin. The

photovoltaic device data was completed by Eric Peterson. The manuscript was prepared

by Christopher M. MacNeill and Robert C. Coffin and edited by David L. Carroll and

Ronald E. Noftle.

116

S

S

O

O

nS

S

O

O

Sn(CH3)3(H3C)3Sn

Pd(PPh3)4

chlorobenzene

200oC, 10 min

P12

microwave S

NO O

C8H17

+

S

N

Br Br

O O

C8H17

38a

35


Polymer P12238-240 was synthesized according to the same procedure outlined in

Chapter 7 and used as the control during this study. The bis-stannylated monomer, 2,6-

bis(trimethyltin)-4,8-bis(2-ethylhexyl-oxy)benzo[1,2-b:4,5-b’]dithiophene (35), was

polymerized with 1,3-dibromo-5-octylthieno[3,4-b]pyrrole-4,6-dione (38a)235-236 in

chlorobenzene under microwave radiation using tetrakis(triphenylphosphine)

palladium(0) (Pd(PPh3)4) as the catalyst to give P12 (Scheme 11). Polymers P13-P14

were synthesized using the same microwave procedure. Reacting 2,6-Bis(trimethyltin)-

4,4-bis(2-ethylhexyl)cyclopenta-[2,1-b;3,4-b’]dithiophene (33),237 with either 1,3-

dibromo-5-octylthieno [3,4-b]pyrrole-4,6-dione (38a) or 1,3-dibromo-5-(2-ethylhexyl)

thieno[3,4-b]pyrro-le-4,6-dione (38b), 235-236 gave polymers P13-P14 (Scheme 12).

Scheme 11: The synthesis of polymer P12.

The polymers were subsequently precipitated, washed with methanol and hexane,

and then extracted with chloroform in a Soxhlet extractor. Gel-permeation

chromatography (135 °C, 1,2,4-trichlorobenzene) of polymer P13 precipitated from the

chloroform extract revealed a number average molecular weight (Mn) of 10.3 kg/mol and

polydispersity index (PDI) of 1.24.

117

+

S

N

Br Br

O O

R

S S SnMe3Me3Sn

S S n

R = n-octyl P13

Pd(PPh3)4

chlorobenzene


R = 2-ethylhexyl P14

S

NO O

R38a-b 33

Scheme 12. The synthesis of polymers P13-P14.

The polymers are very soluble (>10 mg/mL) in chlorinated solvents such as chloroform,

chlorobenzene and dichlorobenzene.



10 °C/min and the results can be seen in Figure 39. P12 is stable up to 280oC, after

which, there is a decrease in weight attributed to the loss of the alkoxy side chains on the

BDT unit (calc., 31.7 %; found, 31.4 %). A second weight decrease is observed between

450 and 500oC, which is attributed to loss of the octyl side chain on the

thienopyrroledione monomer (calc., 15.8 %; found, 15.2 %). The TGA of P12 is

comparable to the literature TGA trace.238 Polymers P13-P14 showed greater thermal

stability, with their onsets of degradation ranging from 375 to 400°C. These results are

consistent with the loss of the ethylhexyl side chains from the CPDT monomer and loss

of either an octyl side chain or an ethylhexyl side chain from the thienopyrroledione

monomer (calculated: P13, 50.3 %, P14; 50.5 %, found: P13; 49.5 %, P14; 51.3 %).

Degradation of the polymer structure was observed after 500oC for all three polymers.

118

0

20

40

60

80

100

120

0 100 200 300 400 500 600

Temperature (oC)

Wei

gh

t %

Figure 39: The TGA curve of P12 (blue), P13 (black) and P14 (red) under argon at

10oC/min.

Differential scanning calorimetry shows no discernable thermal transitions between 0 and

250 °C (Appendix B12) for polymer P13. This indicates that thermal annealing of the

device substrate, in order to align the polymer chains, is not required because the polymer

does not have a glass transition temperature.

9.3. UV-Visible Spectroscopy of P12-P14

Normalized UV-visible absorption spectra of P12, P13 and P14 in chloroform

solution can be seen in Figure 40. The λmax for P12 in solution is 633 nm (lit. 627 nm)239

compared to 653 nm, for polymers P13 and P14. This is due to the lower band gap of the

CPDT donor monomer compared to BDT. The absorption onset for P12 in solution is

119

300 400 500 600 700 800 900

Wavelength (nm)

Ab

sorb

ance

(a.

u.)

685 nm (lit. 685 nm)238 compared to 712 nm for P13-P14, corresponding to an optical

band gap of 1.74 eV, 0.07 eV lower than P12.

Figure 40: The UV-vis absorption spectra of P12 (blue), P13 (black) and P14 (red) in

chloroform solution.


Cyclic voltammetry of drop-cast polymer films was employed to estimate the

HOMO and LUMO energy levels of P12-P14 (Figure 41). The onset of oxidation for P12

was 0.41 V, which corresponds to a HOMO level of -5.21 eV (lit. 5.4 eV).239 The onset

of oxidation of P13-P14 was ~0.27 V corresponding to a HOMO level of -5.07 eV. As

seen in the figure the onset is similar to that for PBDTTPD and because of this a similar

Voc in the OPV devices was anticipated. The onset of reduction for P12-P14 is -1.67 V

which corresponds to a LUMO level of -3.13 eV (lit. - 3.4 eV). This gives an

electrochemical band gap of 2.14 eV for P12 (lit. 2.03, 1.81 eV)238,240 and 1.94 eV for

P13-P14. Table 7 shows the optical and electrochemical characteristics of P12-P14.

120

-2.5 -1.5 -0.5 0.5 1.5

Potential (V vs. Fc/Fc+)

Cu

rre

nt

20µA

Figure 41: The cyclic voltammograms of P12 (blue), P13 (black) and P14 (red) films

drop-cast from chloroform solution.



λmax

(nm) Eg

opt (eV)

Eox onset (V)

HOMO (eV)

Ered onset (V)

LUMO (eV)

Egelect

(eV) P12 633 1.81 0.41 -5.21 -1.67 -3.13 2.14 P13 653 1.74 0.27 -5.07 -1.67 -3.13 1.94 P14 653 1.74 0.27 -5.07 -1.67 -3.13 1.94


The internal structure of the polymers was investigated using X-ray powder

diffraction (Figure 42). For P12, one low intensity peak was seen at 2θ = 5.7. This

corresponds to a d-spacing of 20.8 Å (lit. 20.9 Å)238. This d-spacing relates to the

intermolecular distance between polymer chains in the same plane. The peak at 2θ = 24.8

121

0

20

40

60

80

100

120

140

160

180

200

3 8 13 18 23 28

2θ (degrees)

Inte

nsi

ty

(d2 = 3.60 Å, lit. 3.6 Å238) corresponds to the π-π stacking distance between polymer

chains in adjacent planes. For P13 and P14, similar powder diffraction spectra can be

seen. Four low intensity diffraction peaks were observed at 2θ = 5.7, 7.7, 9.4 for P13 and

2θ = 5.6 and 8.3 for P14. These 2θ values give rise to d1-spacings of 15.6 Å, 11.4 Å, 9.4

Å for P13 and 15.9 Å and 10.6 Å for P14, respectively. The peaks at d1 = 15.6 Å for P13

and 15.9 Å for P14, correspond to the intermolecular distance between polymer chains.

The slight difference in length arises from the different side chains on the TPD acceptor.

For P13, the side chain is an octyl group, while for P14, the side chain is an ethylhexyl

group. The peaks at d3 = 11.4 Å and 10.6 Å, for P13 and P14, respectively, relate to the

second order peak of the powder pattern.

Figure 42: The powder diffraction patterns for P12 (blue), P13 (black) and P14 (red) on

loop.

If the d1 peak corresponds to the (1,0,0) plane, the d3 peak will correspond to the (2,0,0)

plane. This finding is indicative of long range order in the polymer. The peaks at d2 =

d1 = 20.8 Å d1 = 15.9 Å

d3 = 10.6 Å

d1 = 15.6 Å

d3 = 11.4 Å

d2 = 3.67 Å

d2 = 3.77 Å

d2 = 3.60 Å

122

-10

-8

-6

-4

-2

0

2

-0.1 0.1 0.3 0.5 0.7 0.9

Voltage (V)

Cu

rre

nt

De

ns

ity

(m

A/c

m2)

3.77 Å for P13 and 3.67 Å for P14, correspond to the π-π stacking distance between

polymer chains in adjacent planes.

9.6. Photovoltaic Properties of P12 and P13

The photovoltaic characteristics of the polymer were determined using a standard

bulk heterojunction device architecture as reported in Chapters 6-7. The composition of

the device is ITO/PEDOT:PSS/P12-P13:PC61BM/Al. The 0.38 mm2 devices were

fabricated under an inert atmosphere and tested in air. The active layer of P12 was spin-

coated from a chlorobenzene solution (8 mg/mL) with a weight ratio of 1:1.5

P12:PC61BM. The polymer showed a Voc of 0.78 V, a Jsc of 6.51 mA/cm2 and a FF of

0.45 and a PCE of 2.31. Due to the similarity of the results for P13 and P14, only the

photovoltaic characteristics of P13 were investigated (Table 8).

Figure 43: Current-voltage characteristics of BHJ solar cells based on 1:1.5 (w:w)

P12:PC61BM (blue) and 1:2.5 (w:w) P13:PC61BM (black) with 2 % DIO additive.

123

0

10

20

30

40

50

60

350 450 550 650 750

Wavelength (nm)

EQ

E %

The active layer of P13 was deposited from a chlorobenzene solution (9 mg/mL) and the

weight ratio of P13:PC61BM was varied from 1:1 to 1:3 in increments of 0.5 to determine

the optimal fullerene loading. As seen in Table 9, by increasing the P13:PC61BM from

1:1 to 1:2.5, the Voc remains relatively constant while the Jsc increases from 3.95 to 8.02

mA/cm2 and PCE increases from 1.02 to 2.43 %. At 1:3 the device efficiencies

dramatically decrease. In order to further improve device efficiencies, the 1:2.5

P13:PC61BM devices were processed using 2% 1,8-diiodooctane (DIO) as a solvent

additive.237 Figure 43 shows an average of the J-V curves for these devices. Processing

with DIO leads to a decrease in Voc from 0.92 to 0.87 V but improvements in Jsc and fill

factor (FF) lead to an improved average PCE of 3.15 %. The Voc of these devices is

similar to that reported for PBDTTPD238-240 consistent with the HOMO level determined

by CV measurement. The EQE of the DIO processed devices is shown in Figure 44.

Figure 44: External quantum efficiency spectra of BHJ solar cells based on 1:1.5 (w:w)

P12:PC61BM (blue) and 1:2.5 (w:w) P13:PC61BM with 2% DIO additive (black).

124

For P12, The EQE is flat (around ~ 40-45 %) between 475-600 nm. The current

integrates to 7.14 mA/cm2 for the EQE of P12. This is slightly greater than the short

circuit current generated from the device (6.51 mA/cm2). This indicates decent current

production compared to the upper limit of the polymer. The EQE peaks at ~ 45-50 %

between 550 and 675 nm for P13 and current is generated beyond 700 nm.

Table 8: Photovoltaic characteristics of best devices prepared from P12-P13 and

PC61BM.

Voc (V) Jsc (mA/cm2) FF PCE (%)

P12 0.78 6.51 0.45 2.31 P13 0.92 8.02 0.34 2.43

Table 9: A comparison of the photovoltaic characteristics of P13 at different (w:w) ratios

PC61BM and using additive processing. The best device PCE can be seen in parenthesis.

P13:PCBM Voc (V) Jsc (mA/cm2) FF PCE (%)

1:1 0.89 3.95 0.29 1.02 1:1.5 0.92 6.81 0.34 2.05 1:2 0.90 7.65 0.34 2.30

1:2.5 0.92 8.02 0.34 2.43 1:3 0.80 6.24 0.28 1.27

1:2.5 2% DIO 0.87 8.70 0.43 3.15 (3.47)

9.7. Conclusion

In conclusion, we have successfully synthesized a new copolymer, P13, using a

Stille coupling procedure under microwave radiation and compared it to a known

polymer P12. The UV-visible spectrum indicates that the P13 polymer absorbed further

into the red region than P12, indicating a lower band gap. Cyclic voltammetry revealed

125

that the HOMO and LUMO energy levels were consistent with the optical band gap

observed in the absorbance spectrum. Powder x-ray diffraction of P12-P14 showed that

the polymer had long range order. The J-V and EQE curves showed that P13 had a high

Voc (0.92 V) and Jsc (8.02 mA/cm2), and a good PCE (2.43), while the best device in 2%

solvent additive gave a PCE of 3.47. These results indicate that P13 has potential

application as a donor polymer in BHJ solar cells.

126

CONCLUSIONS

There has been on-going research into the study of new materials with

applications in areas such as sustainability, renewability and green technologies. These

materials have become imperative to our survival as a society, now more than ever.

Inorganic/organic polymeric materials, such as coordination polymers for use as

heterogeneous catalysts, may offer a way to make new organic materials in faster time

periods, under milder conditions with a catalyst that can be recycled in subsequent

reactions. Simple filtration and drying allows for the coordination polymer to be re-used

up to three times without loss of activity. Since homogeneous catalalysts are expensive,

difficult to recover, and lose catalytic effectiveness, coordination polymers may provide

environmentally cost-effective synthetic routes.

Nine new lanthanide-based coordination polymers were synthesized and

characterized using a variety of methods such as single crystal x-ray diffraction, powder

diffraction, elemental analysis, TGA, infrared spectroscopy and solid state

photoluminescence. The heterogeneous catalytic activity of coordination polymers 1-2

and 7-9 were assessed in the Biginelli reaction. The Biginelli reaction is a

cyclocondensation reaction of an aldehyde, urea and a dicarbonyl compound to give a

substituted dihydropyrimidinone, which have been used as anti-virals and in other

medicinal applications. Coordination polymers 1-2 showed low yields of

dihydropyrimidinone product in the Biginelli reaction because of the mild basicity of the

frameworks due to the 2,5-thiophenedicarboxylate linker. Coordination polymers 5-9

were synthesized using a less basic linker, 2,3,5,6-tetrafluoroterephthalic acid, and

127

catalytic activity in the Biginelli reaction doubled. These results showed that, by

synthesizing a coordination polymer using a less basic organic linker with electron

withdrawing groups, the lanthanide metal ion became more electropositive and a better

Lewis acid.

Organic polymeric materials promise the same improvements as

inorganic/organic polymeric materials in terms of sustainability and renewability. The

use of organic polymeric materials as photovoltaic devices to harvest sunlight and turn it

into electricity, will help relieve our dependence on foreign oil and cut down on the

release of carbon dioxide gas which contributes to global warming. Today, silicon-based

devices dominate the solar cell market due to their high power conversion efficiencies;

however, organic photovoltaics offer a cheaper alternative to conventional silicon-based

devices, with an ease in processing conditions due to the ability of the organic

photovoltaics to be solution-cast printed or spray-coated.

Twelve new low band gap polymers were synthesized and characterized using a

variety of methods such as 1H-NMR, 13C-NMR, infrared spectroscopy, gel permeation

chromatography, TGA, UV-visible spectroscopy, cyclic voltammetry and powder x-ray

diffraction. Polymers P1 and P2 were insoluble in all common chlorinated solvents. The

molecular weight of polymer P2 increased ten fold when the ethyl branch was moved one

carbon closer to the BDT backbone (P3). This slight change was enough to frustrate

stacking of the polymer in the solid state, enabling it to stay in solution longer and

continue to grow in molecular weight. The soluble donor monomer having a 3-octyl side

chain polymerized with alternate electron-withdrawing co-monomers yielded co-

polymers P4-P6 that were again fairly insoluble. These polymers did show a lower

128

optical and electrochemical band gap than the P3 polymer. Moving from the soluble 3-

octyl side chain donor-acceptor co-polymer P3 to a bulkier 6-undecyl donor-acceptor co-

polymer P7, further increased the molecular weight of the polymer, as well as its solution

processability. Device data showed an increase in EQE from 350-700 nm, as well as an

increase in PCE from ~ 3 % to ~ 3.9 %. Co-polymers P8-P11 were synthesized using

similar electron-acceptor monomers as seen in P4-P6. This lowered the band gap of the

co-polymers while maintaining good solution processability, which was not observed

with co-polymers P4-P6. P11 showed a high Voc along with some crystallinity in the

powder diffraction spectrum so it was further optimized using solvent additives. After

processing with DIO and CN, this polymer-based device showed an improvement from

2.7 % efficiency to a champion efficiency of 6.05 %. With results like these and many

others, the theoretical limit of 10 % PCE for a polymer-based device is on the horizon. It

may only be a matter of time before researchers achieve this feat and polymer solar cell

production is begun on a global scale.

129

FUTURE WORK

Future work for the first project should be to assess the catalytic activity of the

coordination polymers 1-9 in other reactions besides the Biginelli reaction. This may lead

to coordination polymers 1-9 showing better activity in other systems. Other reactions

may include Lewis acid-based catalytic reactions, the Knoevenagel condensation, the

cyanosilylation of aldehydes or the epoxidation of olefins.

New lanthanide-based coordination polymers based on larger organic linkers

should be synthesized and characterized. These new coordination polymers with larger

channel sizes may have their catalytic properties evaluated by the Biginelli reaction. By

varying the size of the organic substrates, one should be able to probe for size selective

catalysis and determine whether catalysis can take place in the channels of the

frameworks instead of on the surface which was observed for coordination polymers 1-9.

Future work for the second project would be to answer some of the questions that

have arisen during the research already conducted. The selenium-based polymers P9 and

P10 showed lower power conversion efficiencies compared to P3-P11. This could be due

to the ability of the selenium acceptor to coordinate palladium. Rigorous steps must be

taken during the polymer workup to remove palladium. Use of palladium coordinating

ligands and celite filtration, combined with quantification of the palladium content in the

polymers using inductively coupled plasma mass spectrometry, may determine whether it

is the palladium that is inhibiting power conversion efficiency of the device.

If there is to be commercialization of organic solar cells which can be placed on

the roofs of houses or windows of buildings, modules will have to be spray-coated. Initial

130

results of spray-coating polymer P11 showed good power conversion efficiencies around

3 %. As of the start of 2011, the world record efficiency for a spray coated device is ~

2.8 %. Despite this fascinating result, optimization of the polymer solar cell devices

should continue in order to achieve greater efficiencies. Using solvent additive processing

with spray coating should help with this optimization.

131

REFERENCES

1. Steed, J. W.; Atwood, J. L. “Encylcopedia of Supramolecular Chemistry”, 2nd Ed. Marcel Dekker Inc., 2004, 1257-1258.

2. “Self Assembly.” In Wikipedia, The Free Encyclopedia. Wikimedia Foundation,

Inc.Web. April 3, 2011. http://en.wikipedia.org/wiki/Self-assembly.

3. Lehn, J.-M. “Supramolecular Chemistry: Concepts and Perspectives.” VCH, 1995, 154.

4. Schnebeck, R.-D.; Freisinger, E.; Lippert, B. “Molecular architecture with 2,2'-bipyrazine and metal ions: Infinite loop and molecular square.” Eur. J. Inorg. Chem. 2000, 6, 1193-1200.

5. Stang, P. J.; Olenyuk, B. “Self-Assembly, Symmetry, and Molecular Architecture: Coordination as the Motif in the Rational Design of Supramolecular Metallacyclic Polygons and Polyhedra.” Acc. Chem. Res. 1997, 30(12), 502-518.

6. Dietrich-Buchecker, C. O.; Sauvage, J. P. “Cloverleaf-knot compounds.” Angew. Chem. 1989, 101(2), 192-194.

7. Fujita, M. “Self-Assembly of [2]Catenanes Containing Metals in Their Backbones.” Acc. Chem. Res. 1999, 32(1), 53-61.

8. Wu, C.; Lecavalier, P. R.; Shen, Y. X.; Gibson, H. W. “Synthesis of a rotaxane via the template method.” Chem. Mater. 1991, 3(4), 569-572.

9. Caulder, D. L.; Raymond, K. N. “The rational design of high symmetry coordination clusters.” Dalton Trans. 1999, 8, 1185-1200.

10. Albrecht, M. “Dicatechol ligands: novel building-blocks for metallo-supramolecular chemistry.” Chem. Soc. Rev. 1998, 27(4), 281-288.

11. Bailar, J. C.; Jolly, W. L. Preparative Inorganic Reactions. Wiley Interscience,

New York, 1964, 1, 1–25. 12. Janiak, C. “Engineering coordination polymers towards applications.” Dalton

Trans. 2003, 14, 2781-2804. 13. Yaghi, O. M.; Li, H. “Hydrothermal Synthesis of a Metal-Organic Framework

Containing Large Rectangular Channels.” J. Am. Chem. Soc. 1995, 117(41), 10401-10402.

132

14. “Coordination polymers.” In Wikipedia, The Free Encyclopedia. Wikimedia Foundation. Web. April 8, 2011 http://en.wikipedia.org/wiki/Coordination polymers.

15. Biradha, K.; Ramanan, A.; Vittal, J. J. “Coordination Polymers Versus Metal-

Organic Frameworks.” Cryst. Growth Des. 2009, 9(7), 2969-2970. 16. Tranchemontagne, D. J.; Mendoza-Cortes, J. L.; O'Keeffe, M.; Yaghi, O. M.

“Secondary building units, nets and bonding in the chemistry of metal-organic frameworks.” Chem. Soc. Rev. 2009, 38(5), 1257-1283.

17. Hu, Y. H.; Zhang, L. “Hydrogen Storage in Metal-Organic Frameworks.” Adv.

Mater. 2010, 22(20), E117-E130. 18. Ma, S.; Zhou, H.-C. “Gas storage in porous metal-organic frameworks for clean

energy applications.” Chem. Commun. 2010, 46(1), 44-53. 19. Ma, L.; Abney, C.; Lin, W. “Enantioselective catalysis with homochiral metal-

organic frameworks.” Chem. Soc. Rev. 2009, 38(5), 1248-1256. 20. Ma, L.; Lin, W. “Designing metal-organic frameworks for catalytic applications.”

Top. Curr. Chem. 2010, 293, 175-205. 21. Corma, A.; Garcia, H.; Llabres i Xamena, F. X. “Engineering Metal Organic

Frameworks for Heterogeneous Catalysis.” Chem. Rev. 2010, 110(8), 4606-4655. 22. Kurmoo, M. “Magnetic metal-organic frameworks.” Chem. Soc. Rev. 2009, 38(5),

1353-1379. 23. Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T. “Luminescent

metal-organic frameworks.” Chem. Soc. Rev. 2009, 38(5), 1330-1352. 24. Keskin, S.; Kizilel, S. “Biomedical Applications of Metal Organic Frameworks.”

Ind. Eng. Chem. Res. 2011, 50(4), 1799-1812. 25. McKinlay, A. C.; Morris, R. E.; Horcajada, P.; Ferey, G.; Gref, R.; Couvreur, P.;

Serre, C. “BioMOFs: Metal-Organic Frameworks for Biological and Medical Applications.” Angew. Chem., Int. Ed. 2010, 49(36), 6260-6266.

26. Liu, Y.; Kravtsov, V.; Walsh, R. D.; Poddar, P.; Srikanth, H.; Eddaoudi, M.

“Directed assembly of metal-organic cubes from deliberately predesigned molecular building blocks.” Chem. Commun. 2004, 24, 2806-2807.

27. Liu, Y.; Kravtsov, V. C.; Beauchamp, D. A.; Eubank, J. F.; Eddaoudi, M. “4-

Connected Metal-Organic Assemblies Mediated via Heterochelation and Bridging

133

of Single Metal Ions: Kagome Lattice and the M6L12 Octahedron.” J. Am. Chem. Soc. 2005, 127(20), 7266-7267.

28. Brant, J. A.; Liu, Y.; Sava, D. F.; Beauchamp, D.; Eddaoudi, M. “Single-metal-

ion-based molecular building blocks (MBBs) approach to the design and synthesis of metal-organic assemblies.” J. Mol. Struct. 2006, 796(1-3), 160-164.

29. Sava, D. F.; Kravtsov, V. C.; Nouar, F.; Wojtas, L.; Eubank, J. F.; Eddaoudi, M.

“Quest for Zeolite-like Metal-Organic Frameworks: On Pyrimidinecarboxylate Bis-Chelating Bridging Ligands.” J. Am. Chem. Soc. 2008, 130(12), 3768-3770.

30. Bauer, C. A.; Timofeeva, T. V.; Settersten, T. B.; Patterson, B. D.; Liu, V. H.;

Simmons, B. A.; Allendorf, M. D. “Influence of Connectivity and Porosity on Ligand-Based Luminescence in Zinc Metal-Organic Frameworks.” J. Am. Chem. Soc. 2007, 129(22), 7136-7144.

31. Dai, F.; He, H.; Gao, D.; Ye, F.; Sun, D.; Pang, Z.; Zhang, L.; Dong, G.; Zhang, C.

“Self-assembly of 2D zinc metal-organic frameworks based on mixed organic ligands.” Inorg. Chim. Acta. 2009, 362(11), 3987-3992.

32. Hu, J.-S.; Shang, Y.-J.; Yao, X.; Qin, L.; Li, Y.-Z.; Guo, Z.-J.; Zheng, H.-G.; Xue,

Z.-L. “Syntheses, Structures, and Photoluminescence of Five New Metal-Organic Frameworks Based on Flexible Tetrapyridines and Aromatic Polycarboxylate Acids.” Cryst. Growth Des. 2010, 10(6), 2676-2684.

33. Liu, C.-S.; Wang, J.-J.; Chang, Z.; Batten, S. R.; Yan, L.-F.; Bu, X.-H.

“Photoluminescent cadmium(II) metal-organic framework based on anthracene-9,10-dicarboxylate exhibiting an unusual (3,4)-connected (6.82)2(6.85) topology.” Trends Inorg. Chem. 2008, 10, 81-89.

34. Nadeem, M. A.; Thornton, A. W.; Hill, M. R.; Stride, J. A. “A flexible copper

based microporous metal-organic framework displaying selective adsorption of hydrogen over nitrogen.” Dalton Trans. 2011, 40(13), 3398-3401.

35. Lysenko, A. B.; Govor, E. V.; Domasevitch, K. V. “Eight-connected coordination

framework supported by tricopper(II) secondary building blocks.” Inorg. Chim. Acta. 2007, 360(1), 55-60.

36. Taylor, K. M. L.; Rieter, W. J.; Lin, W. “Manganese-Based Nanoscale Metal-

Organic Frameworks for Magnetic Resonance Imaging.” J. Am. Chem. Soc. 2008, 130(44), 14358-14359.

37. Ladrak, T.; Smulders, S.; Roubeau, O.; Teat, S. J.; Gamez, P.; Reedijk, J.

“Manganese-Based Metal-Organic Frameworks as Heterogeneous Catalysts for the Cyanosilylation of Acetaldehyde.” Eur. J. Inorg. Chem. 2010, 24, 3804-3812.

134

38. Wong-Foy, A. G.; Matzger, A. J.; Yaghi, O. M. “Exceptional H2 Saturation Uptake in Microporous Metal-Organic Frameworks.” J. Am. Chem. Soc. 2006, 128(11), 3494-3495.

39. Panella, B.; Hirscher, M.; Puetter, H.; Mueller, U. “Hydrogen adsorption in metal-

organic frameworks: Cu-MOFs and Zn-MOFs compared.” Adv. Funct. Mater. 2006, 16(4), 520-524.

40. Chen, B.; Ockwig, N. W.; Millward, A. R.; Contreras, D. S.; Yaghi, O. M. “High

H2 adsorption in a microporous metal-organic framework with open metal sites.” Angew. Chem., Int. Ed. 2005, 44(30), 4745-4749.

41. Lin, X.; Jia, J.; Zhao, X.; Thomas, K. M.; Blake, A. J.; Walker, G. S.; Champness,

N. R.; Hubberstey, P.; Schroeder, M. “High H2 adsorption by coordination-framework materials.” Angew. Chem., Int. Ed. 2006, 45(44), 7358-7364.

42. Chen, B.-L.; Mok, K.-F.; Ng, S.-C.; Drew, M. G. B. “Thiophene-2,5-dicarboxylic

acid incorporated self-assembly of one-, two- and three-dimensional coordination polymers.” New J. Chem. 1999, 23(8), 877-883.

43. Chen, B.-L.; Mok, K.-F.; Ng, S.-C.; Drew, M. G. B. “Syntheses, structures and

properties of copper(II) complexes with thiophene-2,5-dicarboxylic acid (H2Tda) and nitrogen-containing ligands.” Polyhedron. 1999, 18(8,9), 1211-1220.

44. Sun, X.-Z.; Sun, Y.-F.; Ye, B.-H.; Chen, X.-M. “Hydrogen-bonding organization

of (4,4) coordination layers into a 3-D molecular architecture with channels clathrating guest molecules [Cu(tdc)(bpy)(H2O)](bpy) (tdc = thiophene-2,5-dicarboxylate; bpy = 4,4'-bipyridine).” Inorg. Chem. Commun. 2003, 6(11), 1412-1414.

45. Chen, B.-L.; Mok, K.-F.; Ng, S.-C.; Feng, Y.-L.; Liu, S.-X. “Synthesis,

characterization and crystal structures of three diverse copper(II) complexes with thiophene-2,5-dicarboxylic acid and 1,10-phenanthroline.” Polyhedron. 1998, 17(23-24), 4237-4247.

46. Jia, H.-P.; Li, W.; Ju, Z.-F.; Zhang, J. “Synthesis, structure and magnetism of

metal-organic framework materials with doubly pillared layers.” Eur. J. Inorg. Chem. 2006, 21, 4264-4270.

47. Sun, X.-Z.; Huang, Z.-L.; Wang, H.-Z.; Ye, B.-H.; Chen, X.-M. “Syntheses and

crystal structures of cadmium complexes with thiophene-dicarboxylate and bipyridine-like ligands.” Z. Anorg. Allg. Chem. 2005, 631(5), 919-923.

48. Deng, Z. P.; Gao, S.; Huo, L. H.; Zhao, H. “catena-Poly[[aquadiimidazole

cadmium(II)]-thiophene-2,5-dicarboxylato]. Acta Crystallogr., Sec. E: Struct. Rep. Online. 2006, E62(1), m87-m89.

135

49. Abourahma, H.; Bodwell, G. J.; Lu, J.; Moulton, B.; Pottie, I. R.; Bailey Walsh, R.;

Zaworotko, M. J. “Coordination Polymers from Calixarene-Like [Cu2(Dicarboxylate)2]4 Building Blocks: Structural Diversity via Atropisomerism.” Cryst. Growth Des. 2003, 3(4), 513-519.

50. Rosi, N. L.; Kim, J.; Eddaoudi, M.; Chen, B.; O'Keeffe, M.; Yaghi, O. M. “Rod

Packings and Metal-Organic Frameworks Constructed from Rod-Shaped Secondary Building Units.” J. Am. Chem. Soc. 2005, 127(5), 1504-1518.

51. James, S. L. “Metal-organic frameworks.” Chem. Soc. Rev. 2003, 32(5), 276-88. 52. Zhao, J.; Wang, X.-L.; Shi, X.; Yang, Q.-H.; Li, C. “Synthesis, Structure, and

Photoluminescent Properties of Metal-Organic Coordination Polymers Assembled with Bithiophenedicarboxylic Acid.” Inorg. Chem. 2011, 50(8), 3198-3205.

53. Bureekaew, S.; Sato, H.; Matsuda, R.; Kubota, Y.; Hirose, R.; Kim, J.; Kato, K.;

Takata, M.; Kitagawa, S. “Control of Interpenetration for tuning structural flexibility influences sorption properties.” Angew. Chem., Int. Ed. 2010, 49(42), 7660-7664.

54. Rowsell, J. L. C.; Yaghi, O. M. “Effects of Functionalization, Catenation, and

Variation of the Metal Oxide and Organic Linking Units on the Low-Pressure Hydrogen Adsorption Properties of Metal-Organic Frameworks.” J. Am. Chem. Soc. 2006, 128(4), 1304-1315.

55. Koh, K.; Wong-Foy, A. G.; Matzger, A. J. “A Porous Coordination Copolymer

with over 5000 m2/g BET Surface Area.” J. Am. Chem. Soc. 2009, 131(12), 4184-4185.

56. Johnson, J. “E. V. Murphree Award in Industrial & Engineering Chemistry.”

Chem. Eng. News. 2004, 82(4), 61. 57. Yong, Z.; Mata, V.; Rodrigues, A. E. “Adsorption of carbon dioxide at high

temperature. A review.” Sep. Purif. Tech. 2002, 26(2-3), 195-205. 58. Ruthven, D. M. Encyclopedia of Separation Technology, John Wiley Inc., New

York, 1997, 1, 94–129, 59. Song, H. K.; Lee, K. H. “Adsorption of carbon dioxide on chemically modified

carbon adsorbents.” Sep. Sci. Technol. 1998, 33(13), 2039–2057. 60. Yong, Z.; Mata, V.; Rodrigues, A. E. “Adsorption of carbon dioxide on

chemically modified high surface area carbon based adsorbents at high temperatures.” Adsorption. 2001, 7(1), 41-50.

136

61. Auroux, A.; Gervasini, A. “Microcalorimetric study of the acidity and basicity of metal oxides surface.” J. Phys. Chem. 1990, 94, 6371-6379.

62. Norman, N. L. Preprints of Topical Conference on Separation Science and

Technologies, Los Angeles, CA, 1997, 5-7. 63. Couck, S.; Denayer, J. F. M.; Baron, G. V.; Remy, T.; Gascon, J.; Kapteijn, F.

“An Amine-Functionalized MIL-53 Metal-Organic Framework with Large Separation Power for CO2 and CH4.” J. Am. Chem. Soc. 2009, 131(18), 6326-6327.

64. Ahnfeldt, T.; Gunzelmann, D.; Loiseau, T.; Hirsemann, D.; Senker, J.; Ferey, G.;

Stock, N. “Synthesis and Modification of a Functionalized 3D Open-Framework Structure with MIL-53 Topology.” Inorg. Chem. 2009, 48(7), 3057-3064.

65. Llewellyn, P. L.; Bourrelly, S.; Serre, C.; Vimont, A.; Daturi, M.; Hamon, L.; De

Weireld, G.; Chang, J.-S.; Hong, D.-Y.; Hwang, Y. K.; Jhung, S. H.; Ferey, G. “High Uptakes of CO2 and CH4 in Mesoporous Metal-Organic Frameworks MIL-100 and MIL-101.” Langmuir. 2008, 24(14), 7245-7250.

66. Banerjee, R.; Phan, A.; Wang, B.; Knobler, C.; Furukawa, H.; O'Keeffe, M.;

Yaghi, O. M. “High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture.” Science. 2008, 319(5865), 939-943.

67. Rowsell, J. L. C.; Yaghi, O. M. “Effects of Functionalization, Catenation, and

Variation of the Metal Oxide and Organic Linking Units on the Low-Pressure Hydrogen Adsorption Properties of Metal-Organic Frameworks.” J. Am. Chem. Soc. 2006, 128(4), 1304-1315.

68. Furukawa, H.; Yaghi, O. M. “Storage of Hydrogen, Methane, and Carbon Dioxide

in Highly Porous Covalent Organic Frameworks for Clean Energy Applications.” J. Am. Chem. Soc. 2009, 131(25), 8875-8883.

69. Millward, A. R.; Yaghi, O. M. “Metal-Organic Frameworks with Exceptionally

High Capacity for Storage of Carbon Dioxide at Room Temperature.” J. Am. Chem. Soc. 2005, 127(51), 17998-17999.

70. Wong-Foy, A. G.; Matzger, A. J.; Yaghi, O. M. “Exceptional H2 Saturation

Uptake in Microporous Metal-Organic Frameworks.” J. Am. Chem. Soc. 2006, 128(11), 3494-3495.

71. Baldi, A.; Dam, B. “Thin film metal hydrides for hydrogen storage applications.” J.

Mater. Chem. 2011, 21(12), 4021-4026. 72. Fichtner, M. “Nanotechnological aspects in materials for hydrogen storage.” Adv.

Eng. Mater. 2005, 7(6), 443-455.

137

73. Orimo, S.-I.; Nakamori, Y.; Eliseo, J. R.; Zuttel, A.; Jensen, C. M “Complex

hydrides for hydrogen storage.” Chem. Rev. 2007, 107(10), 4111-32. 74. Bogdanovic, B.; Schwickardi, M. “Ti-doped alkali metal aluminum hydrides as

potential novel reversible hydrogen storage materials.” J. Alloys Compd. 1997, 253-254, 1-9.

75. Arean, C. O.; Palomino, G. T.; Garrone, E.; Nachtigallova, D.; Nachtigall, P.

“Combined Theoretical and FTIR Spectroscopic Studies on Hydrogen Adsorption on the Zeolites Na-FER and K-FER.” J. Phys. Chem. B. 2006, 110(1), 395-402.

76. Golberg, D.; Bando, Y.; Tang, C.; Zhi, C. “Boron nitride nanotubes.” Adv. Mater.

2007, 19(18), 2413-2432. 77. Schlapbach, L.; Zuettel, A. “Hydrogen-storage materials for mobile applications.”

Nature. 2001, 414(6861), 353-358. 78. Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A.

O.; Snurr, R. Q.; O'Keeffe, M.; Kim, J.; Yaghi, O. M. “Ultrahigh Porosity in Metal-Organic Frameworks.” Science. 2010, 329(5990), 424-428.

79. Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.; Kim, J.; O'Keeffe, M.; Yaghi,

O. M. “Hydrogen Storage in Microporous Metal-Organic Frameworks.” Science. 2003, 300(5622), 1127-1130.

80. Collins, D. J.; Zhou, H.-C. “Hydrogen storage in metal-organic frameworks.” J.

Mater. Chem. 2007, 17(30), 3154-3160. 81. Li, X.; Zhang, Y.-B.; Shi, M.; Li, P.-Z. “(4,4)- and (6,3)-2-D luminescent

lanthanide(III) metal-organic frameworks constructed from tetrafluorosuccinate and 1,10-phenanthroline.” Inorg. Chem. Commun. 2008, 11(8), 869-872.

82. Yang, X.-P.; Jones, R. A.; Rivers, J. H.; Lai, R. P. “Syntheses, structures and

luminescent properties of new lanthanide-based coordination polymers based on 1,4-benzenedicarboxylate (bdc).” Dalton Trans. 2007, 35, 3936-3942.

83. Bai, Y.; He, G.-J.; Zhao, Y.-G.; Duan, C.-Y.; Dang, D.-B.; Meng, Q.-J. “Porous

material for absorption and luminescent detection of aromatic molecules in water.” Chem. Commun. 2006, 14, 1530-1532.

84. Chen, B.; Wang, L.; Zapata, F.; Qian, G.; Lobkovsky, E. B. “A Luminescent

Microporous Metal-Organic Framework for the Recognition and Sensing of Anions.” J. Am. Chem. Soc. 2008, 130(21), 6718-6719.

138

85. Chen, B.; Yang, Y.; Zapata, F.; Lin, G.; Qian, G.; Lobkovsky, E. B. “Luminescent open metal sites within a metal-organic framework for sensing small molecules.” Adv. Mater. 2007, 19(13), 1693-1696.

86. Harbuzaru, B. V.; Corma, A.; Rey, F.; Atienzar, P.; Jorda, J. L.; Garcia, H.;

Ananias, D.; Carlos, L. D.; Rocha, J. “Metal-organic nanoporous structures with anisotropic photoluminescence and magnetic properties and their use as sensors.” Angew. Chem., Int. Ed. 2008, 47(6), 1080-1083.

87. Wu, J.-Y.; Yeh, T.-T.; Wen, Y.-S.; Twu, J.; Lu, K.-L. “Unusual Robust

Luminescent Porous Frameworks Self-Assembled from Lanthanide Ions and 2,2'-Bipyridine-4,4'-dicarboxylate.” Cryst. Growth Des. 2006, 6(2), 467-473.

88. Zucchi, G.; Maury, O.; Thuery, P.; Ephritikhine, M. “Structural diversity in

neodymium bipyrimidine compounds with near infrared luminescence: from mono- and binuclear complexes to metal-organic frameworks.” Inorg. Chem. 2008, 47(22), 10398-406.

89. Stokes, G. G. Philosophical Transactions of the Royal Society of London. 1852,

142, 463. 90. Gispert, J. R. Coordination Chemistry. Wiley-VCH. 2008, 483. 91. Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T. “Luminescent

metal-organic frameworks.” Chem. Soc. Rev. 2009, 38(5), 1330-1352. 92. Tong, M.-L.; Yu, X.-L.; Chen, X.-M. “Synthesis and structure of a

photoluminescent three-dimensional network [AgL(MeCN)] (L = 4,5-dichloro-2-cyano-3,6-dione-1,4-cyclohexen-1-ol anion).” Inorg. Chem. Commun. 2000, 3(12), 694-696.

93. Dai, J.-C.; Wu, X.-T.; Fu, Z.-Y.; Cui, C.-P.; Hu, S.-M.; Du, W.-X.; Wu, L.-M.;

Zhang, H.-H.; Sun, R.-Q. “Synthesis, Structure, and Fluorescence of the Novel Cadmium(II)-Trimesate Coordination Polymers with Different Coordination Architectures.” Inorg. Chem. 2002, 41(6), 1391-1396.

94. Fun, H.-K.; Raj, S. S.; Xiong, R.-G.; Zuo, J.-L.; Yu, Z.; You, X.-Z. “A three-

dimensional network coordination polymer, (terephthalato)(pyridine)cadmium, with blue fluorescent emission.” Dalton Trans. 1999, 12, 1915-1916.

95. Sabbatini, N.; Guardigli, M.; Lehn, J. M. “Luminescent lanthanide complexes as

photochemical supramolecular devices.” Coord. Chem. Rev. 1993, 123(1-2), 201-28.

139

96. Yu, L.-Q.; Huang, R.-D.; Xu, Y.-Q.; Liu, T.-F.; Chu, W.; Hu, C.-W. “Syntheses, structures and properties of novel 3D lanthanide metal-organic frameworks with paddle-wheel building blocks.” Inorg. Chim. Acta. 2008, 361(7), 2115-2122.

97. Thirumurugan, A.; Natarajan, S. “Assembly of a Secondary Building Unit (SBU)

into Two- and Three-Dimensional Structures in Lanthanide Benzene-dicarboxylates.” Cryst. Growth Des. 2006, 6(4), 983-988.

98. Yang, X.-P.; Jones, R. A.; Rivers, J. H.; Lai, R. P. “Syntheses, structures and

luminescent properties of new lanthanide-based coordination polymers based on 1,4-benzenedicarboxylate (bdc).” Dalton Trans. 2007, 35, 3936-3942.

99. Fujita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. “Preparation, Clathration Ability,

and Catalysis of a Two-Dimensional Square Network Material Composed of Cadmium(II) and 4,4'-Bipyridine.” J. Am. Chem. Soc. 1994, 116(3), 1151-2.

100. Schlichte, K.; Kratzke, T.; Kaskel, S. “Improved synthesis, thermal stability and

catalytic properties of the metal-organic framework compound Cu3(BTC)2.” Microporous Mesoporous Mater. 2004, 73(1-2), 81-88.

101. Horike, S.; Dinca, M.; Tamaki, K.; Long, J. R. “Size-Selective Lewis Acid

Catalysis in a Microporous Metal-Organic Framework with Exposed Mn2+ Coordination Sites.” J. Am. Chem. Soc. 2008, 130(18), 5854-5855.

102. Evans, O. R.; Ngo, H. L.; Lin, W. “Chiral porous solids based on lamellar

lanthanide phosphonates.” J. Am. Chem. Soc. 2001, 123(42), 10395-10396. 103. Hurst, E. W. “Experimental chemotherapy of infection with agents of the

psittacosis-lymphogranuloma-trachoma group.” Ann. N.Y. Acad. Sci. 1962, 98(1), 275-278, discussion 278-286.

104. Kappe, C. O. “Biologically active dihydropyrimidones of the Biginelli-type - a

literature survey.” Eur. J. Med. Chem. 2000, 35(12), 1043-1052. 105. Kappe, C. O. “100 Years of the Biginelli dihydropyrimidine synthesis.”

Tetrahedron. 1993, 49(32), 6937-63. 106. Kappe, C. O. “Recent Advances in the Biginelli Dihydropyrimidine Synthesis.

New Tricks from an Old Dog.” Acc. Chem. Res. 2000, 33(12), 879-888. 107. Bao, S.-S.; Ma, L.-F.; Wang, Y.; Fang, L.; Zhu, C.-J.; Li, Y.-Z.; Zheng, L.-M.

“Anion-directed self-assembly of lanthanide-notp compounds and their fluorescence, magnetic, and catalytic properties.” Chem. Eur. J. 2007, 13(8), 2333-2343.

140

108. Wang, C.-M.; Wu, Y.-Y.; Chang, Y.-W.; Lii, K.-H. “Luminescent lanthanide oxalatophosphites with a three-dimensional framework structure: [Ln(H2O)(C2O4)0.5(HPO3)] H2O (Ln = Pr, Nd, and Sm-Lu).” Chem. Mater. 2008, 20(9), 2857-2859.

109. Wang, C.-M.; Wu, Y.-Y.; Hou, C.-H.; Chen, C.-C.; Lii, K.-H. “Synthesis,

Characterization, and Properties of Organically Templated Lanthanide Oxalatophosphates with a Three-Dimensional Honeycomb Structure: (H4APPIP)[Ln3(C2O4)5.5(H2PO4)2] 5H2O (Ln = Er-Lu, APPIP = 1,4-Bis(3-aminopropyl)piperazine).” Inorg. Chem. 2009, 48(4), 1519-1523.

110. Hasegawa, S.; Horike, S.; Matsuda, R.; Furukawa, S.; Mochizuki, K.; Kinoshita,

Y.; Kitagawa, S. “Three-Dimensional Porous Coordination Polymer Functionalized with Amide Groups Based on Tridentate Ligand: Selective Sorption and Catalysis.” J. Am. Chem. Soc. 2007, 129(9), 2607-2614.

111. Gascon, J.; Aktay, U.; Hernandez-Alonso, M. D.; van Klink, G. P. M.; Kapteijn, F.

“Amino-based metal-organic frameworks as stable, highly active basic catalysts.” J. Catal. 2009, 261(1), 75-87.

112. Kaye, S. S.; Dailly, A.; Yaghi, O. M.; Long, J. R. “Impact of Preparation and

Handling on the Hydrogen Storage Properties of Zn4O(1,4-benzenedicarboxylate)3 (MOF-5).” J. Am. Chem. Soc. 2007, 129(46), 14176-14177.

113. G. M. Sheldrick, SADABS, version 2.03, Bruker AXS Inc., Madison, WI, 2001. 114. G. M. Sheldrick, SHELXTL, version 6.12, Bruker AXS Inc., Madison, WI, 2001. 115. GADDS, version 4.1.14 “General Area Detector Diffraction System Program for

Instrument Control and Data Collection” BRUKER AXS Inc., Madison, WI. 116. EVA V8.0 “Graphics Program for 2-dimensional Data evaluation and

Presentation” BRUKER AXS Inc., Madison, WI. 117 Hu, D.-X.; Luo, F.; Che, Y.-X.; Zheng, J.-M. “Construction of Lanthanide Metal-

Organic Frameworks by Flexible Aliphatic Dicarboxylate Ligands Plus a Rigid m-Phthalic Acid Ligand.” Cryst. Growth Des. 2007, 7(9), 1733-1737.

118. Ying, S.-M.; Mao, J.-G. “Introducing a Second Ligand: New Route to

Luminescent Lanthanide Polyphosphonates.” Cryst. Growth Des. 2006, 6(4), 964-968.

119. Thirumurugan, A.; Natarajan, S. “Inorganic-organic hybrid compounds: Synthesis

and structures of new metal organic polymers synthesized in the presence of mixed dicarboxylates.” Eur. J. Inorg. Chem. 2004, 4, 762-770. b) Marsh, R. E.

141

“P1 or Pī? or something else?” Acta Cryst., Sec. B: Str. Sci. 1999, B55(6), 931-936.

120 Zheng, X.-J.; Jin, L.-P.; Gao, S.; Lu, S.-Z. “Second ligand-directed self-assembly

of lanthanide(III) coordination polymers with 1,4-naphthalenedicarboxylate.” New J. Chem. 2005, 29(6), 798-804.

121. Hong, X.-L.; Li, Y.-Z.; Hu, H.; Pan, Y.; Bai, J.; You, X.-Z. “Synthesis, Structure,

Luminescence, and Water Induced Reversible Crystal-to-Amorphous Transformation Properties of Lanthanide(III) Benzene-1,4-dioxylacetates with a Three-Dimensional Framework.” Cryst. Growth Des. 2006, 6(6), 1221-1226.

122. Spek, A.L. PLATON, Version 1.62. University of Utrecht, 1999.

123. Wang, J.-G.; Huang, C.-C.; Huang, X.-H.; Liu, D.-S. “Three-Dimensional Lanthanide Thiophenedicarboxylate Framework with an Unprecedented (4,5)-Connected Topology.” Cryst. Growth Des. 2008, 8(3), 795-798.

124. Gong, Y.; Wang, T.; Zhang, M.; Hu, C. W. “Synthesis, structure and property of

metal thiophene-2,5-dicarboxylates: Novel three dimensional coordination polymers.” J. Mol. Struct. 2007, 833(1-3), 1-7.

125. Yang, E.-C.; Zhao, H.-K.; Ding, B.; Wang, X.-G.; Zhao, X.-J. “Four Novel Three-

Dimensional Triazole-Based Zinc(II) Metal-Organic Frameworks Controlled by the Spacers of Dicarboxylate Ligands: Hydrothermal Synthesis, Crystal Structure, and Luminescence Properties.” Cryst. Growth Des. 2007, 7(10), 2009-2015.

126. Valeur, B. Molecular Fluorescence: Principles and Application. Wiley-VCH.

Weinheim, 2002. 127. Yersin, H.; Vogler, A. Photochemistry and Photophysics of Coordination

Compounds. Springer, Berlin, 1987. 128. Gu, X.; Xue, D. “Incorporating Metal Clusters into Three-Dimensional Ln(III)-

Cu(I) Coordination Frameworks through Linear Ligands.” Cryst. Growth Des. 2007, 7(9), 1726-1732.

129. Yue, Q.; Yang, J.; Li, G.-H.; Li, G.-D.; Xu, W.; Chen, J.-S.; Wang, S.-N. “Three-

Dimensional 3d-4f Heterometallic Coordination Polymers: Synthesis, Structures, and Magnetic Properties.” Inorg. Chem. 2005, 44(15), 5241-5246.

130. Wu, J.-Y.; Yeh, T.-T.; Wen, Y.-S.; Twu, J.; Lu, K.-L. “Unusual Robust

Luminescent Porous Frameworks Self-Assembled from Lanthanide Ions and 2,2'-Bipyridine-4,4'-dicarboxylate.” Cryst. Growth Des. 2006, 6(2), 467-473.

142

131. Zhu, X.; Gao, S.; Li, Y.; Yang, H.; Li, G.; Xu, B.; Cao, R. “Syntheses, structures and photoluminescence of a series of lanthanide-organic frameworks involving in situ ligand formation.” J. Solid State Chem. 2009, 182(3), 421-427.

132. Li, X.; Zhang, Y.-B.; Shi, M.; Li, P.-Z. “(4,4)- and (6,3)-2-D luminescent

lanthanide(III) metal-organic frameworks constructed from tetrafluorosuccinate and 1,10-phenanthroline.” Inorg. Chem. Commun. 2008, 11(8), 869-872.

133. de Lill, D. T; de Bettencourt-Dias, A.; Cahill, C. L. “Exploring lanthanide

luminescence in metal-organic frameworks: synthesis, structure, and guest-sensitized luminescence of a mixed europium/terbium-adipate framework and a terbium-adipate framework.” Inorg. Chem. 2007, 46(10), 3960-5.

134. Zhang, Z.-H.; Song, Y.; Okamura, T.; Hasegawa, Y.; Sun, W.-Y.; Ueyama, N.

“Syntheses, Structures, Near-Infrared and Visible Luminescence, and Magnetic Properties of Lanthanide-Organic Frameworks with an Imidazole-Containing Flexible Ligand.” Inorg. Chem. 2006, 45(7), 2896-2902.

135. Sun, Y.-Q.; Zhang, J.; Chen, Y.-M.; Yang, G.-Y. “Porous lanthanide-organic open

frameworks with helical tubes constructed from interweaving triple-helical and double-helical chains.” Angew. Chem., Int. Ed. 2005, 44(36), 5814-5817.

136. Hasegawa, Y.; Yamamuro, M.; Wada, Y.; Kanehisa, N.; Kai, Y.; Yanagida, S.

“Luminescent Polymer Containing the Eu(III) Complex Having Fast Radiation Rate and High Emission Quantum Efficiency.” J. Phys. Chem. A. 2003, 107(11), 1697-1702.

137. Ma, Y.; Qian, C.; Wang, L.; Yang, M. “Lanthanide Triflate Catalyzed Biginelli

Reaction. One-Pot Synthesis of Dihydropyrimidinones under Solvent-Free Conditions.” J. Org. Chem. 2000, 65(12), 3864-3868.

138. Wang, M.; Xie, M.-H.; Wu, C.-D.; Wang, Y.-G. “From one to three: a serine

derivate manipulated homochiral metal-organic framework.” Chem. Commun. 2009, 17, 2396-2398.

139. Yang, T.-H.; Zhou, K.; Bao, S.-S.; Zhu, C.-J.; Zheng, L.-M. “Syntheses, structures

and catalytic properties of one-dimensional lanthanide -dotp compounds [dotpH8 = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis-(methylenephosphonic acid)].” Inorg. Chem. Commun. 2008, 11(9), 1075-1078.

140 Liu, X.-G.; Zhou, K.; Dong, J.; Zhu, C.-J.; Bao, S.-S.; Zheng, L.-M. “Homochiral

Lanthanide Phosphonates with Brick-Wall-Shaped Layer Structures Showing Chiroptical and Catalytical Properties.” Inorg. Chem. 2009, 48(5), 1901-1905.

141. The size of the aldehydes were determined using Spartan ES V. 2.0.1.

Wavefunction, Inc.

143

142. Gandara, F.; Garcia-Cortes, A.; Cascales, C.; Gomez-Lor, B.; Gutierrez-Puebla, E.;

Iglesias, M.; Monge, A.; Snejko, N. “Rare Earth Arenedisulfonate Metal-Organic Frameworks: An Approach toward Polyhedral Diversity and Variety of Functional Compounds.” Inorg. Chem. 2007, 46(9), 3475-3484.

143. Ravon, U.; Domine, M.. E.; Gaudillere, C.; Desmartin-Chomel, A.; Farrusseng, D.

“MOF-5 as acid catalyst with shape selectivity properties.” Stud. Surf. Sci. Catal. 2008, 174A, 467-470.

144. Li, L. G.; Lu, G. H.; Yang, X. N.; Zhou, E. L. “Progress in polymer solar cell.”

Chin. Sci. Bull. 2007, 52(2), 145-158. 145. In Key World Energy Statistics, International Energy Agency, 2006. www.iea.org

146. Ameri, T.; Dennler, G.; Lungenschmied, C.; Brabec, C. J. “Organic tandem solar cells: a review.” Energy Environ. Sci. 2009, 2(4), 347-363.

147. Goldemberg, E. J.; Johansson, T. B. World Energy Assessment Overview, Update,

United Nations Development Programme, New York, 2004. www.undp.org/ energy/weaover2004.htm.

148. Hoffman, W. “PV solar electricity industry: Market growth and perspective.”

Sol. Energy Mater. Sol. Cells. 2006, 90(18-19), 3285-3311. 149. Nielsen, T. D.; Cruickshank, C.; Foged, S.; Thorsen, J.; Krebs, F. C. “Business,

market and intellectual property analysis of polymer solar cells.” Sol. Energy Mater. Sol. Cells. 2010, 94(10), 1553-1571.

150. Sears, F. W., Zemansky, M. W.; Young, H. D. University Physics, Sixth Edition,

Addison-Wesley, 1983, 843-844. 151. Dana, J. D.; Dana, E.S. Am. J. Sci. 1880, 234 152 Einstein, A. “Heuristic viewpoint on the production and conversion of light.”

Annalen der Physik. 1905, 17, 132-148. 153. Einstein, A. “Motion of suspended particles in stationary liquids required from the

molecular kinetic theory of heat.” Annalen der Physik. 1905, 17, 549-560. 154. Becquerel, A. E. "Recherches sur les effets de la radiation chimique de la lumiere

solaire au moyen des courants electriques." Compt. Rend. Acad. Sci. 1839, 9, 145-149. "Mémoire sur les effets électriques produits sous l'influence des rayons solaires." Compt. Rend. Acad. Sci. 1839, 9, 561-567.

155. Smith, W. Nature. 1873, 7, 303.

144

156. Adams, W. G.; Day, R. E. Proc. R. Soc. London. 1876, 25, 113. 157. Bergmann, L. Phys. Z. 1931, 32, 286-288. 158. Hallwachs, P. Phys. Z. 1904, 5, 489. 159. Arnodal, L. O.; Geiger, P. H. Trans. AIEE. 1927, 46, 357. 160. Schottky, W.; Deutschmann, W. Phys. Z. 1928, 30, 839. 161. Lange, B. Phys. Z. 1928, 31, 139. 162. Adler, E. “The photovoltaic effect.” J. Chem. Phys. 1941, 9, 486. 163. Fritts, C. E. Proc. Am. Ass. Adv. Sci. 1883, 33, 97; Am. J. Sci. 1883, 26, 465. 164. In Silicon P-N Junction. 1999, ScienCentral Inc. and American Institute of

Physics. http://www.pbs.org/transistor/science/events/pnjunc.html 165. Chapin, D. M.; Fuller, C. S.; Pearson, G. L. “A new silicon p-n junction photocell

for converting solar radiation into electrical power.” J. Appl. Phys. 1954, 25, 676-677.

166. Green, M. A.; Emery, K.; King, D. L.; Igari, S.; Warta, W. “Solar cell efficiency

tables (version 22).” Prog. Photovoltaics. 2003, 11(5), 347-352. 167. Green, M. A.; Emery, K.; King, D. L.; Igari, S.; Warta, W. “Solar cell efficiency

tables (version 25).” Prog. Photovoltaics. 2005, 13(1), 49-54. 168. Shockley, W.; Queisser, H. J. “Detailed balance limit of efficiency of p-n junction

solar cells.” J. Appl. Phys. 1961, 32, 510-519. 169. Green, M. A. “Solar Cells: Operating Principles, Technology and System

Applications.” Prentice-Hall, Englewood Cliffs, NJ, 1982. 170. Goetzberger, A.; Hebling, C.; Chock, H. W. “Photovoltaic materials, history,

status and outlook. Mater. Sci. Eng., R: Rep. 2003, R40(1), 1-46. 171. Green, M. A. Recent developments in photovoltaics. Sol. Energy 2004, 76(1-3),

3-8. 172. Green, M. A. “Third generation photovoltaics: solar cells for 2020 and beyond.”

Physica E. 2002, 14(1-2), 65-70.

145

173. Nielsen, T. D.; Cruickshank, C.; Foged, S.; Thorsen, J.; Krebs, F. C. “Business, market and intellectual property analysis of polymer solar cells.” Sol. Energy Mater. Sol. Cells. 2010, 94(10), 1553-1571.

174. Green, M. A.; Emery, K.; Hishikawa, Y.; Warta, W. “Solar cell efficiency tables

(version 34).” Prog. Photovoltaics. 2009, 17(5), 320-326. 175. Volmer, M. “Different Photoelectric Phenomena in Anthracene, their Relation to

one another, to Fluorescence and to the Formation of Dianthracene.” Annalen der Physik. 1913, 40, 775-96.

176. Pochettino, A. “Photoelectric behavior of anthracene.” Acad. Lincei Rend. 1906,

15, 355-363. 177. Bube, R. H. Photoconductivity of Solids, Wiley, New York, 1960. 178. Anthoe, S. Organic photovoltaic cells: a review. Rom. Rep. Phys. 2002, 53(3-8),

427-449. 179. R. F. Cozzens, in: D.A. Seanor, Electrical Properties of Polymer, Academic

Press, New York, 1982, 93.

180. Shirakawa, H.; Louis, E. J.; MacDiarmid, A. G.; Chiang, C. K.; Heeger A. J. “Synthesis of electrically conducting organic polymers: halogen derivatives of polyacetylene, (CH)x.” Chem. Commun. 1977, 16, 578-80.

181. Chiang, C. K.; Fincher, C. R.; Park, Y. W.; Heeger, A. J.; Shirakawa, H.; Louis, E. “J. Electrical conductivity in doped polyacetylene.” Phys. Rev. Lett. 1977, 39(17), 1098-101.

182. Weinberger, B. R.; Akhtar, M.; Gau, S. C. “Polyacetylene photovoltaic devices.” Synth. Met. 1982, 4(3), 187-97.

183. Glenis, S.; Tourillon, G.; Garnier, F. “Influence of the doping on the photovoltaic

properties of thin films of poly-3-methylthiophene.” Thin Solid Films. 1986, 39(3), 221-31.

184. Karg, S.; Riess, W.; Dyakonov, V.; Schwoerer, M. “Electrical and optical

characterization of poly(phenylene-vinylene) light emitting diodes.” Synth. Met. 1993, 54(1-3), 427-33.

185. Yu, G.; Gao, J.; Hummelen, J. C.; Wudl, F.; Heeger, A. J. “Polymer photovoltaic

cells: enhanced efficiencies via a network of internal donor-acceptor heterojunctions.” Science. 1995, 270(5243), 1789-91.

146

186. Sariciftci, N. S.; Smilowitz, L.; Heeger, A. J.; Wudl, F. “Semiconducting polymers (as donors) and buckminsterfullerene (as acceptor): photoinduced electron transfer and heterojunction devices.” Synth. Met. 1993, 59(3), 333-52.

187. Sariciftci, N. S.; Braun, D.; Zhang, C.; Srdanov, V. I.; Heeger, A. J.; Stucky, G.;

Wudl, F. “Semiconducting polymer-buckminsterfullerene heterojunctions: diodes, photodiodes, and photovoltaic cells.” Appl. Phys. Lett. 1993, 62(6), 585-7.

188. Schilinsky, P.; Waldauf, C.; Brabec, C. J. “Recombination and loss analysis in

polythiophene based bulk heterojunction photodetectors.” Appl. Phys. Lett. 2002, 81(20), 3885-3887.

189. Kim, K.; Liu, J.; Namboothiry, M. A. G.; Carroll, D. L. “Roles of donor and

acceptor nanodomains in 6% efficient thermally annealed polymer photovoltaics.” Appl. Phys. Lett. 2007, 90(16), 163511/1-163511/3.

190. Reyes-Reyes, M.; Kim, K.; Carroll, D. L. “High-efficiency photovoltaic devices

based on annealed poly(3-hexylthiophene) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 blends.” Appl. Phys. Lett. 2005, 87(8), 083506/1-083506/3.

191. Scharber, M. C.; Muhlbacher, D.; Koppe, M.; Denk, P.; Waldauf, C.; Heeger, A.

J.; Brabec, C. J. “Design rules for donors in bulk-heterojunction solar cells-towards 10 % energy-conversion efficiency.” Adv. Mater. 2006, 18(6), 789-794.

192. Koster, L. J. A.; Mihailetchi, V. D.; Blom, P. W. M. “Ultimate efficiency of

polymer/fullerene bulk heterojunction solar cells.” Appl. Phys. Lett. 2006, 88(9), 093511/1-093511/3.

193. Kietzke, T. “Recent advances in organic solar cells.”Adv. OptoElectronics. 2007,

40285/1-40285/15. 194. Blom, P. W. M.; Mihailetchi, V. D.; Koster, L. J. A.; Markov, D. E. “Device

physics of polymer:fullerene bulk heterojunction solar cells.” Adv. Mater. 2007, 19(12), 1551-1566.

195. Stubinger, T.; Brutting, W. J. “Exciton diffusion and optical interference in

organic donor-acceptor photovoltaic cells.” J. Appl. Phys. 2001, 90(7), 3632-3641.

196. Savenije, T. J.; Warman, J. M.; Goossens, A. “Visible light sensitization of

titanium dioxide using a phenylene vinylene polymer.” Chem. Phys. Lett. 1998, 287(1-2), 148-153.

197. Parker, I. “Carrier tunneling and device characteristics in polymer light-emitting

diodes.” J. Appl. Phys. 1994, 75(3), 1656-66.

147

198. Coakley, K. M.; McGehee, M. D. “Conjugated Polymer Photovoltaic Cells.” Chem. Mater. 2004, 16(23), 4533-4542.

199. Brabec, C. J.; Cravino, A.; Meissner, D.; Saricifitci, N. S.; Fromherz, T.; Minse,

M.; Sanchez, L.; Hummelen, J. C. “Origin of the open circuit voltage of plastic solar cells.” Adv. Funct. Mater. 2001, 11(5), 374-380.

200. Baruch, P.; De Vos, A.; Landsberg, P. T.; Parrott, J. E. “On some thermodynamic

aspects of photovoltaic solar energy conversion.” Sol. Energy Mater. Sol. Cells. 1995, 36(2), 201-22.

201. Hung, L. S.; Tang, C. W.; Mason, N. G. “Enhanced electron injection in organic

electroluminescence devices using an Al/LiF electrode.” Appl. Phys. Lett. 1997, 70(2), 152-154.

202. Jabbour, G. E.; Kawabe, Y.; Shaheen, S.; Wang, J. F.; Morell, M. M.; Kippelen,

B.; Peyghembarian, N. “Highly efficient and bright organic electroluminescent devices with an aluminum cathode.” Appl. Phys. Lett. 1997, 71(13), 1762-1764.

203. de Jong, M. P.; Friedlein, R.; Osikowicz, W.; Salaneck, W. R.; Fahlman, M.

“Ultraviolet photoelectron spectroscopy of polymers.” Mol. Cryst. Liq. Cryst. 2006, 455, 193-203.

204. Groenendaal, L. B.; Jonas, F.; Freitag, D.; Pielartzik, H.; Reynolds, J. R.

“Poly(3,4-ethylenedioxythiophene) and its derivatives: past, present, and future.” Adv. Mater. 2000, 12(7), 481-494.

205. Uchida, J. X.; Rand, B. P.; Forrest, S. R. “Organic small molecule solar cells with

a homogeneously mixed copper phthalocyanine: C60 active layer.” Appl. Phys. Lett. 2004, 84(21), 4218-4220.

206. Zhou, X.; Blochwitz, J.; Pfeiffer, M.; Nollau, A.; Fritz, T.; Leo, K. “Enhanced

hole injection into amorphous hole-transport layers of organic light-emitting diodes using controlled p-type doping.” Adv. Funct. Mater. 2001, 11(4), 310-314.

207. Wohrle, D.; Meissner, D. “Organic solar cells.” Adv. Mater. 1991, 3(3), 129-38. 208. Halls, J. J. M.; Pichler, K.; Friend, R. H.; Moratti, S. C.; Holmes, A. B. “Exciton

diffusion and dissociation in a poly(p-phenylenevinylene)/C60 heterojunction photovoltaic cell.” Appl. Phys. Lett. 1996, 68(22), 3120-3122.

209. Cheng, Y. J.; Yang, S.-H.; Hsu, C.-S. “Synthesis of Conjugated Polymers for

Organic Solar Cell Applications.” Chem. Rev. 2009, 109(11), 5868-5923.

148

210. Dennler, G.; Scharber, M. C.; Ameri, T.; Denk, P.; Forberich, K.; Waldauf, C.; Brabec, C. J. “Design rules for donors in bulk-heterojunction tandem solar cells-towards 15 % energy-conversion efficiency.” Adv. Mater. 2008, 20(3), 579-583.

211. Hiramoto, M.; Suezaki, M.; Yokoyama, M. “Effect of thin gold interstitial-layer

on the photovoltaic properties of tandem organic solar cell.” Chem. Lett. 1990, 3, 327-30.

212. Kawano, K.; Ito, N.; Nishimori, T.; Sakai, J. “Open circuit voltage of stacked bulk

heterojunction organic solar cells.” Appl. Phys. Lett. 2006, 88(7), 073514/1-073514/3.

213. Dennler, G.; Prall, H. J.; Koeppe, R.; Egginger, M.; Autengruber, R.; Sariciftci, N.

S. “Enhanced spectral coverage in tandem organic solar cells.” Appl. Phys. Lett. 2006, 89(7), 073502/1-073502/3.

214. Kim, J. Y.; Lee, K.; Coates, N. E.; Moses, D.; Nguyen, T. Q.; Dante, M.; Heeger,

A. J. “Efficient Tandem Polymer Solar Cells Fabricated by All-Solution Processing.” Science. 2007, 317(5835), 222-225.

215. Wudl, F. “The chemical properties of buckminsterfullerene (C60) and the birth

and infancy of fulleroids.” Acc. Chem. Res. 1992, 25, 157-161. 216. Allemond, P. M.; Koch, A.; Wudl, F.; Rubin, Y.; Diederich, F.; Alvarez, M. M.;

Anz, S. J.; Whetten, R. L. “Two different fullerenes have the same cyclic voltammetry.” J. Am. Chem. Soc. 1991, 113, 1050-1051.

217. Brabec, C. J.; Zerza, G.; Cerullo, G.; Silvestre, S. D.; Luzatti, S.; Hummelen, J. C.;

Sariciftci, N. S. “Tracing photoinduced electron transfer process in conjugated polymer/fullerene bulk heterojunctions in real time.” Chem. Phys. Lett. 2001, 340, 232-236.

218. Nunzi, J. M. Organic photovoltaic materials and devices. C.R. Physique. 2002, 3,

523-542. 219. Bundgaard, E.; Krebs, F. C. Low band gap polymers for organic photovoltaics.

Sol. Energy. Mater. Sol. Cells. 2007, 91, 954-985. 220. Minnaert, B.; Burgelman, M. “Efficiency potential of organic bulk heterojunction

solar cells.” Prog. Photovoltaics. 2007, 15(8), 741-748. 221. Thompson, B. C.; Frechet, J. M. “Polymer-fullerene composite solar cells.”

Angew. Chem. Int. Ed. 2008, 47, 58-77. 222. Brabec, C. J.; Winder, C.; Sariciftci, N. S.; Hummelen, J. C.; Dhanabalan, A.; van

Hal, P. A.; Janssen, R. A. J. “A low-bandgap semiconducting polymer for

149

photovoltaic devices and infrared emitting diodes.” Adv. Funct. Mater. 2002, 12, 709-712.

223. Winder, C.; Matt, G.; Hummelen, J. C.; Janssen, R. A.; Sariciftci, N. S.; Brabec,

C. J. “Sensitization of low bandgap polymer bulk heterojunction solar cells.” Thin Solid Films. 2002, 403-404, 373-379.

224. Shaheen, S. E.; Brabec, C. J.; Sariciftci, N. S.; Padinger, F.; Fromherz,

T.; Hummelen, J. C. “2.5% efficient organic plastic solar cells.” Appl. Phys. Lett. 2001, 78, 841-843.

225. Padinger, F.; Rittberger, R. S.; Sariciftci, N. S. “Effects of postproduction treatment on plastic solar cells.” Adv. Funct. Mater. 2003, 13, 85-88.

226. Waldauf, C.; Schilinsky, P.; Hauch, J.; Brabec, C. J. “Material and device

concepts for organic photovoltaics: towards competitive efficiencies.” Thin Solid Films. 2004, 451-452, 503-507.

227. Kim, K.; Liu, J.; Namboothiry, M. A. G.; Carroll, D. L. “Roles of donor and

acceptor nanodomains in 6% efficient thermally annealed polymer photovoltaics.” Appl. Phys. Lett. 2007, 90(16), 163511/1-163511/3.

228. Li, Y. F.; Cao, Y.; Gao, J.; Wang, D. L.; Yu, G.; Heeger, A. J. “Electrochemical

properties of luminescent polymers and polymer light-emitting electrochemical cells.” Synth. Met. 1999, 99, 243-248.

229. Pilgram, K.; Zupan, M.; Skiles, R. “Bromination of 2,1,3-benzothiadiazoles.” J.

Heterocycl. Chem. 1970, 7, 629-633. 230. Fukumoto, H.; Yamamoto, T. “Preparation and chemical properties of soluble

.pi.-conjugated poly(aryleneethynylene) consisting of azabenzothiadiazole as the electron-accepting unit.” J. Poly. Sci. Part A. Poly. Chem. 2008, 46, 2975-2982.

231. Tsubata, Y.; Suzuki, T.; Miyashi, T.; Yamashita, Y. “Single-component organic

conductors based on neutral radicals containing the pyrazino-TCNQ skeleton.” J. Org. Chem. 1992, 57, 6749-6755.

232. Blouin, N.; Michaud, A.; Gendron, D.; Wakim, S.; Blair, E.; Neagu-Plesu, R.;

Belletete, M.; Durocher, G.; Tao, Y.; Leclerc, M. “Toward a Rational Design of Poly(2,7-Carbazole) Derivatives for Solar Cells.” J. Am. Chem. Soc. 2008, 130, 732-742.

233. Hou, J.; Park, M.-H. ; Zhang, S.; Yao, Y.; Chen, L.-M.; Li, J.-H.; Yang, Y.

Bandgap and Molecular Energy Level Control of Conjugated Polymer Photovoltaic Materials Based on Benzo[1,2-b:4,5-b']dithiophene. Macromolecules 2008, 41, 6012-6018.

150

234. Hou, J.; Chen, H.-Y.; Zhang, S.; Chen, R. I.; Yang, Y.; Wu, Y.; Li, G. “Synthesis

of a Low Band Gap Polymer and Its Application in Highly Efficient Polymer Solar Cells. J. Am. Chem. Soc. 2009, 131, 15586-15587.

235. Nielsen, C. B.; Bjornholm, T. “New Regiosymmetrical Dioxopyrrolo- and

Dihydropyrrolo-Functionalized Polythiophenes.” Org. Lett. 2004, 6, 3381-3384. 236. MacDowell, D. W. H.; Wisowaty, J. C. “Thiophene analogs of anthraquinone.” J.

Org. Chem. 1972, 37(11), 1712-17. 237. Lee, J. K.; Ma, W. L.; Brabec, C. J.; Yuen, J.; Moon, J. S.; Kim, J. Y.; Lee, K.;

Bazan, G. C.; Heeger, A. J. “Processing Additives for Improved Efficiency from Bulk Heterojunction Solar Cells.” J. Am. Chem. Soc. 2008, 130(11), 3619-3623.

238. Zou, Y.; Najari, A.; Berrouard, P.; Beaupre, S.; Reda Aich, B.; Tao, Y.; Leclerc,

M. “A Thieno[3,4-c]pyrrole-4,6-dione-Based Copolymer for Efficient Solar Cells.” J. Am. Chem. Soc. 2010, 132(15), 5330-5331.

239. Piliego, C.; Holcombe, T. W.; Douglas, J. D.; Woo, C. H.; Beaujuge, P. M.;

Frechet, J. M. J. “Synthetic Control of Structural Order in N-Alkylthieno[3,4-c]pyrrole-4,6-dione-Based Polymers for Efficient Solar Cells.” J. Am. Chem. Soc. 2010, 132(22), 7595-7597.

240. Zhang, Y.; Hau, S. K.; Yip, H.-L.; Sun, Y.; Acton, O.; Jen, A. K. Y. “Efficient

Polymer Solar Cells Based on the Copolymers of Benzodithiophene and Thienopyrroledione.” Chem. Mater. 2010, 22(9), 2696-2698.

241. Coffin, R. C.; Peet, J.; Rogers, J.; Bazan, G. C. “Streamlined microwave-assisted

preparation of narrow-bandgap conjugated polymers for high-performance bulk heterojunction solar cells.” Nature Chem. 2009, 1, 657-661.

242. Zhou, H.; Yang, L.; Price, S. C.; Knight, K. J.; You, W. “Enhanced Photovoltaic

Performance of Low-Bandgap Polymers with Deep LUMO Levels.” Angew. Chem. Int. Ed. 2010, 49, 7992-7995.

243. Galbrect, F.; Bunnagel, T. W.; Scherf, U.; Farrell, T. “Microwave-assisted

preparation of semiconducting polymers.” Macromol. Rapid Commun. 2007, 29, 387-394.

244. Nehls, B. S. “Semiconducting polymers via microwave-assisted Suzuki and Stille

cross-coupling reactions.” Adv. Funct. Mater. 2004, 14, 352-356. 245. Carter, K. “Nickel(0)-Mediated Coupling Polymerizations via Microwave-

Assisted Chemistry.” Macromolecules. 2002, 35, 6757-6759.

151

246. Peet, J.; Kim, J. Y.; Coates, N. E.; Ma, W. L.; Moses, D.; Heeger, A. J.; Bazan, G. C. “Efficiency enhancement in low-bandgap polymer solar cells by processing with alkane dithiols.” Nature Mater. 2007, 6, 497-500.

247. Peet, J.; Cho, N. S.; Lee, S. K.; Bazan, G. C. “Transition from Solution to the

Solid State in Polymer Solar Cells Cast from Mixed Solvents.” Macromolecules, 2008, 41, 8655-8659.

248. Cossiell, R. F.; Akcelrud, L.; Atvars, D. Z. “Solvent and molecular weight effects

on fluorescence emission of MEH-PPV.” J. Braz. Chem. Soc. 2005, 16, 74-86. 249. Yamamoto, T.; Fang, Q.; Morikita, T. “New Soluble Poly(aryleneethynylene)s

Consisting of Electron-Accepting Benzothiadiazole Units and Electron-Donating Dialkoxybenzene Units. Synthesis, Molecular Assembly, Orientation on Substrates, and Electrochemical and Optical Properties.” Macromolecules. 2003, 36, 4262-4267.

250. Yamamoto, T.; Komarudin, D.; Arai, M.; Lee, B.-L.; Suganuma, H.; Asakawa,

N.; Inoue, Y.; Kubota, K.; Sasaki, S.; Fukuda, T.; Matsuda, H. “Extensive Studies on .pi.-Stacking of Poly(3-alkylthiophene-2,5-diyl)s and Poly(4-alkylthiazole-2,5-diyl)s by Optical Spectroscopy, NMR Analysis, Light Scattering Analysis, and X-ray Crystallography. J. Am. Chem. Soc. 1998, 120, 2047-2058.

251. Watanabe, J.; Harkness, B. R.; Sone, M.; Ichimura, H. “Rigid-rod polyesters with

flexible side chains. 4. Thermotropic behavior and phase structures in polyesters based on 1,4-dialkyl esters of pyromellitic acid and 4,4'-biphenol.” Macromolecules. 1994, 27, 507-512.

252. Kline, R. J.; McGehee, M. D.; Kadnikova, E. N.; Liu, J.; Fréchet, J. M. J.; Toney,

M. F. “Dependence of Regioregular Poly(3-hexylthiophene) Film Morphology and Field-Effect Mobility on Molecular Weight.” Macromolecules 2005, 38, 3312-3319.

253. Chu, T.-Y.; Lu, J.; Beaupre, S.; Zhang, Y.; Pouliot, J.-R.; Wakim, S.; Zhou, J.;

Leclerc, M.; Li, Z.; Ding, J.; Tao, Y. Bulk heterojunction solar cells using thieno[3,4-c]pyrrole-4,6-dione and dithieno[3,2-b:2',3'-d]silole copolymer with a power conversion efficiency of 7.3%. J. Am. Chem. Soc. 2011, 133(12), 4250-4253.

254. Bouffard, J.; Swager, T. M. “Fluorescent conjugated polymers that incorporate

substituted 2,1,3-benzooxadiazole and 2,1,3-benzothiadiazole units.” Macromolecules. 2008, 41(15), 5559-5562.

255. Padhy, H.; Huang, J.-H.; Sahu, D.; Patra, D.; Kekuda, D.; Chu, C.-W.; Lin, H.-C.

“Synthesis and applications of low-bandgap conjugated polymers containing

152

phenothiazine donor and various benzodiazole acceptors for polymer solar cells.” J. Polym. Sci. Part A: Polym. Chem. 2010, 48, 4823-4834.

256. Yang, R.; Tian, R.; Hou, Q.; Yang, W.; Cao, Y. “Synthesis and Optical and

Electroluminescent Properties of Novel Conjugated Copolymers Derived from Fluorene and Benzoselenadiazole.” Macromolecules. 2003, 36, 7453-7460.

257. Jung, I. H.; Kim, H.; Park, M. J.; Kim, B.; Park, J. H.; Jeong, E.; Woo, H. Y.; Yoo,

S.; Shim, H. K. “Synthesis and characterization of cyclopentadithiophene-based low bandgap copolymers containing electron-deficient benzoselenadiazole derivatives for photovoltaic devices.” J. Polym. Sci. Part A: Polym. Chem. 2010, 48, 1423-1432.

258. Huang, F.; Hou, L.; Shen, H.; Yang, R.; Hou, Q.; Cao, Y. “Synthesis and optical

and electroluminescent properties of novel conjugated polyelectrolytes and their neutral precursors derived from fluorene and benzoselenadiazole.” J. Polym. Sci. Part A: Polym. Chem. 2006, 44, 2521-2532.

259. Ono, K.; Tanaka, S.; Yamashita, Y. “Benzobis(thiadiazoles) with hypervalent

sulfur atoms: novel heterocycles with high electron affinities and short intermolecules distances between heteroatoms.” Angew. Chem. 1994, 106(19), 2030-2032, (See also Angew. Chem., Int. Ed. 1994, 33(19), 1977-1979.

260. Fukumoto, H.; Yamamoto, T. “Preparation and chemical properties of

soluble .pi.-conjugated poly(aryleneethynylene) consisting of azabenzothiadiazole as the electron-accepting unit.” J. Polym. Sci. Part A: Polym. Chem. 2008, 46, 2975-2982.

261. Krebs, F. C.; Nyberg, R. B.; Jorgensen, M. “Influence of Residual Catalyst on the

Properties of Conjugated Polyphenylenevinylene Materials: Palladium Nanoparticles and Poor Electrical Performance.” Chem. Mater. 2004, 16, 1313-1318.

262. Li, G.; Yao, Y.; Yang, H.; Shrotriya, V.; Yang, G.; Yang, Y. “"Solvent annealing"

effect in polymer solar cells based on poly(3-hexylthiophene) and methanofullerenes.” Adv. Funct. Mater. 2007, 17, 1636-1644.

263. Zhao, Y.; Xie, Z.; Qu, Y,; Geng, Y.; Wang, L. “Solvent-vapor treatment induced

performance enhancement of poly(3-hexylthiophene):methanofullerene bulk-heterojunction photovoltaic cells.” Appl. Phy. Lett. 2007, 90, 043504/1-043504/3.

264. Lee, J. K.; Ma, W. L.; Brabec, C. J.; Yuen, J.; Moon, J. S.; Kim, J. Y.; Bazan, G.

C.; Heeger, A. J. “Processing Additives for Improved Efficiency from Bulk Heterojunction Solar Cells.“ J. Am. Chem. Soc. 2008, 130, 3619-3623.

153

265. Bijleveld, J. C.; Shalid, M.; Gilot, J.; Wienk, M. M.; Janssen, R. A. J. “Copolymers of Cyclopentadithiophene and Electron-Deficient Aromatic Units Designed for Photovoltaic Applications.” Adv Funct. Mater. 2009, 19, 3262-3270.

154

APPENDIX A: CRYSTAL STRUCTURES FOR COMPOUNDS (1-9),

A full hemisphere of diffracted intensities for compounds (1-9) was measured

using graphite- monochromated MoKα radiation (= 0.71073 Å) on a Bruker SMART

APEX CCD Single Crystal Diffraction System. Lattice constants were determined with

the Bruker SAINT software package. The Bruker software package SHELXTL was used

to solve the structure using “direct methods” techniques. The data was corrected for

variable absorption effects using SADABS. All stages of weighted full-matrix least-

squares refinement were conducted using Fo2 data with the SHELXTL software package.

The resulting structural parameters have been refined to convergence using counter-

weighted full-matrix least-squares techniques and a structural model which incorporated

anisotropic thermal parameters for all nonhydrogen atoms.

Crystallographic data for compounds (1), (2), and (5)-(9) have been deposited in

the Cambridge Crystallographic Data Centre: 720500, 720501, 768795-768799. These

data can be obtained free of charge via the internet at www.ccdc.cam.ac.uk/data_request

/cif, by email at [email protected]., or by contacting the Cambridge Crysta-

llographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-

336033.

155

APPENDIX A1: CRYSTAL STRUCTURE TABLES AND FIGURES FOR COMPOUND (1) [La2(C6H2O4S)3(ONC3H7)2(H2O)-ONC3H7]

Wake Forest University X-Ray Code: a69l

Table A1-1. Crystal data and structure refinement for La2(C6H2O4S)3(ONC3H7)2

(H2O)-ONC3H7

________________________________________________________________________

Identification code a69l

Empirical formula C27 H29 La2 N3 O16 S3

Formula weight 1025.53

Temperature 223(2) K

Wavelength 0.71073 Å

Crystal system Orthorhombic Space group Pna2(1) – C 9

2v (No. 33)

Unit cell dimensions a = 17.434(4) Å

b = 11.227(3) Å

c = 17.980(4) Å.

Volume 3519.0(15) Å3

Z 4

Density (calculated) 1.936 g/cm3

Absorption coefficient 2.649 mm-1

F(000) 2008

Crystal size 0.16 x 0.07 x 0.02 mm3

Theta range for data collection 3.81 to 27.50°

Index ranges -22≤h≤22, -14≤k≤14, -23≤l≤22

Independent reflections 8041 [R(int) = 0.0878]

Completeness to theta = 27.50° 99.7 %

Absorption correction Multi-scan (SADABS)

Max. and min. transmission 0.9489 and 0.6766

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 8041 / 37 / 470

Goodness-of-fit on F2 1.072

Final R indices [I>2sigma(I)] R1 = 0.0542, wR2 = 0.1145

R indices (all data) R1 = 0.0665, wR2 = 0.1200

Largest diff. peak and hole 3.593 and -1.537 e-/Å3

________________________________________________________________________

156

Table A1-2. Bond lengths [Å] and angles [°] for La2(C6H2O4S)3(ONC3H7)2(H2O)-ONC3H7

________________________________________________________________________

La(1)-O(23)#1 2.391(6)

La(1)-O(21) 2.400(6)

La(1)-O(13)#2 2.492(6)

La(1)-O(31) 2.502(6)

La(1)-O(1) 2.549(8)

La(1)-O(33)#3 2.553(6)

La(1)-O(12)#4 2.564(6)

La(1)-O(34)#3 2.869(6)

La(2)-O(11)#5 2.470(6)

La(2)-O(14) 2.536(6)

La(2)-O(34)#6 2.538(6)

La(2)-O(22) 2.539(6)

La(2)-O(24)#7 2.569(6)

La(2)-O(2) 2.587(7)

La(2)-O(4) 2.675(5)

La(2)-O(13) 2.926(7)

La(2)-O(32) 2.430(6)

S(1)-C(11) 1.699(9)

S(1)-C(14) 1.723(9)

S(2)-C(24) 1.698(8)

S(2)-C(21) 1.714(9)

S(3)-C(34) 1.701(8)

S(3)-C(31) 1.708(9)

O(11)-C(15) 1.253(11)

O(12)-C(15) 1.246(11)

O(13)-C(16) 1.245(10)

O(14)-C(16) 1.275(11)

O(21)-C(25) 1.260(12)

O(22)-C(25) 1.244(12)

O(23)-C(26) 1.261(11)

O(24)-C(26) 1.263(11)

O(31)-C(35) 1.270(11)

O(32)-C(35) 1.260(11)

O(33)-C(36) 1.272(11)

O(34)-C(36) 1.255(10)

C(11)-C(12) 1.392(10)

C(11)-C(15) 1.514(10)

C(12)-C(13) 1.414(10)

C(13)-C(14) 1.373(11)

C(14)-C(16) 1.471(11)

C(21)-C(22) 1.371(10)

C(21)-C(25) 1.492(11)

C(22)-C(23) 1.419(11)

C(23)-C(24) 1.378(11)

C(24)-C(26) 1.482(11)

C(31)-C(32) 1.354(10)

C(31)-C(35) 1.490(10)

C(32)-C(33) 1.398(10)

C(33)-C(34) 1.368(10)

C(34)-C(36) 1.469(10)

O(1)-C(1) 1.259(13)

O(2)-C(4) 1.237(12)

O(3)-C(7) 1.216(16)

N(1)-C(1) 1.284(14)

N(2)-C(4) 1.311(14)

N(3)-C(7) 1.328(17)

N(1)-C(2) 1.44(2)

N(1)-C(3) 1.48(2)

N(2)-C(5) 1.424(18)

N(2)-C(6) 1.457(16)

N(3)-C(9) 1.44(2)

N(3)-C(8) 1.502(19)

O(4)-H(41) 0.80(10)

O(23)#1-La(1)-O(21) 131.6(2)

O(23)#1-La(1)-O(13)#2 73.2(2)

O(21)-La(1)-O(13)#2 154.5(2)

157

O(23)#1-La(1)-O(31) 80.4(2)

O(21)-La(1)-O(31) 91.1(2)

O(13)#2-La(1)-O(31) 87.3(2)

O(23)#1-La(1)-O(1) 140.4(2)

O(21)-La(1)-O(1) 76.5(2)

O(13)#2-La(1)-O(1) 79.0(2)

O(31)-La(1)-O(1) 70.7(2)

O(23)#1-La(1)-O(33)#3 79.5(2)

O(21)-La(1)-O(33)#3 73.2(2)

O(13)#2-La(1)-O(33)#3 124.3(2)

O(31)-La(1)-O(33)#3 134.6(2)

O(1)-La(1)-O(33)#3 140.0(2)

O(23)#1-La(1)-O(12)#4 129.9(2)

O(21)-La(1)-O(12)#4 83.2(2)

O(13)#2-La(1)-O(12)#4 82.6(2)

O(31)-La(1)-O(12)#4 142.2(2)

O(1)-La(1)-O(12)#4 71.7(2)

O(33)#3-La(1)-O(12)#4 79.3(2)

O(23)#1-La(1)-O(34)#3 67.58(19)

O(21)-La(1)-O(34)#3 115.2(2)

O(13)#2-La(1)-O(34)#3 77.01(18)

O(31)-La(1)-O(34)#3 147.2(2)

O(1)-La(1)-O(34)#3 132.1(2)

O(33)#3-La(1)-O(34)#3 47.62(18)

O(12)#4-La(1)-O(34)#3 64.55(19)

O(32)-La(2)-O(11)#5 139.9(2)

O(32)-La(2)-O(14) 74.8(2)

O(11)#5-La(2)-O(14) 88.4(2)

O(32)-La(2)-O(34)#6 149.5(2)

O(11)#5-La(2)-O(34)#6 69.6(2)

O(14)-La(2)-O(34)#6 122.1(2)

O(32)-La(2)-O(22) 91.0(2)

O(11)#5-La(2)-O(22) 77.0(2)

O(14)-La(2)-O(22) 137.3(2)

O(34)#6-La(2)-O(22) 90.2(2)

O(32)-La(2)-O(24)#7 83.8(2)

O(11)#5-La(2)-O(24)#7 128.4(2)

O(14)-La(2)-O(24)#7 77.6(2)

O(34)#6-La(2)-O(24)#7 76.59(19)

O(22)-La(2)-O(24)#7 141.7(2)

O(32)-La(2)-O(2) 72.6(2)

O(11)#5-La(2)-O(2) 133.3(2)

O(14)-La(2)-O(2) 138.2(2)

O(34)#6-La(2)-O(2) 79.5(2)

O(22)-La(2)-O(2) 68.7(2)

O(24)#7-La(2)-O(2) 73.5(2)

O(32)-La(2)-O(4) 69.6(3)

O(11)#5-La(2)-O(4) 70.5(2)

O(14)-La(2)-O(4) 69.9(3)

O(34)#6-La(2)-O(4) 137.7(3)

O(22)-La(2)-O(4) 67.4(3)

O(24)#7-La(2)-O(4) 142.2(3)

O(2)-La(2)-O(4) 120.1(2)

O(32)-La(2)-O(13) 117.2(2)

O(11)#5-La(2)-O(13) 69.0(2)

O(14)-La(2)-O(13) 46.85(19)

O(34)#6-La(2)-O(13) 75.28(18)

O(22)-La(2)-O(13) 145.9(2)

O(24)#7-La(2)-O(13) 65.36(19)

O(2)-La(2)-O(13) 135.5(2)

O(4)-La(2)-O(13) 103.0(2)

158

Table A1-3. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x

103) for La2(C6H2O4S)3(ONC3H7)2(H2O)-ONC3H7

________________________________________________________________________

x y z U(eq)

________________________________________________________________________

H(12) -6180 4144 8309 32

H(13) -6363 5137 7102 35

H(22) -2086 10499 3270 38

H(23) -2243 11372 2018 39

H(32) -4660 9702 7114 44

H(33) -4810 10701 8314 42

H(1) -1705 11461 4450 55

H(2A) -1772 13404 4110 115

H(2B) -1230 14185 4621 115

H(2C) -2130 14235 4731 115

H(3A) -1628 12488 6245 89

H(3B) -2023 13707 6019 89

H(3C) -1118 13582 5988 89

H(4) -3811 10979 5125 43

H(5A) -5062 11423 3709 141

H(5B) -4550 12406 3318 141

H(5C) -5122 12771 3963 141

H(6A) -3164 12543 4667 90

H(6B) -3664 13545 4280 90

H(6C) -3254 12560 3791 90

H(7) -4306 4736 5470 76

H(8A) -3042 3429 6648 131

H(8B) -3439 2161 6606 131

H(8C) -3688 3083 7228 131

H(9A) -5195 3295 5871 186

H(9B) -5089 3159 6742 186

H(9C) -4831 2117 6203 186

H(41) -3210(60) 6530(80) 5390(60) 31

________________________________________________________________________

159

Table A1-4. Hydrogen bonds for La2(C6H2O4S)3(ONC3H7)2(H2O)-ONC3H7 [Å and °].

________________________________________________________________________

D-H...A d(D-H) d(H...A) d(D...A) <(DHA)

________________________________________________________________________

O(4)-H(41)...O(3) 0.80(10) 2.02(10) 2.777(11) 156(10)

________________________________________________________________________ Figure A1-1: A view of the asymmetric unit of La2(C6H2O4S)3(ONC3H7)2(H2O)-ONC3H7

with nonhydrogen atoms represented by thermal vibration ellipsoids drawn to encompass 50% of their electron density. Hydrogen atoms omitted for clarity.

160

Figure A1-2: A view of the framework of La2(C6H2O4S)3(ONC3H7)2(H2O)-ONC3H7 with

nonhydrogen atoms represented by arbitrarily small spheres, which are in no way representative of their true thermal motion. Hydrogen atoms omitted for clarity.

Figure A1-3: A view of the framework of La2(C6H2O4S)3(ONC3H7)2(H2O)-ONC3H7

projected down the a-axis with nonhydrogen atoms represented by arbitrarily small spheres, which are in no way representative of their true thermal motion. Hydrogen atoms omitted for clarity.

161

APPENDIX A2: CRYSTAL STRUCTURE TABLES AND FIGURES FOR COMPOUND (2) [Gd2(C6H2O4S)3(OCHNMe2)2(H2O)]

Wake Forest University X-Ray Code: a23m

Table A2-1 Crystal Data and Structure refinement for Gd2(C6H2O4S)3(OCHNMe2)2

(H2O) ________________________________________________________________________

Identification code a23m2m

Empirical formula C24 H22 Gd2 N2 O15 S3




Crystal system Monoclinic

Space group P21/n [an alternate setting of P21/c – C2h5


b = 10.8038(11) Å, β = 104.793(2)°

c = 17.7283(18) Å

Volume 3247.9(6) Å3

Z 4



F(000) 1904



Index ranges -21≤h≤21, -13≤k≤13, -21≤l≤21




Ratio Min/Max transmission 0.720921




Final R indices [I>2σ(I)] R1 = 0.0487, wR2 = 0.0956



________________________________________________________________________

162

Table A2-2. Bond lengths [Å] and angles [°] for Gd2(C6H2O4S)3(OCHNMe2)2(H2O)

________________________________________________________________________

Gd(1)-O(1) 2.306(5)

Gd(1)-O(2A) 2.323(5)

Gd(1)-O(3A)#1 2.347(5)

Gd(1)-O(4A)#2 2.359(6)

Gd(1)-O(5) 2.373(5)

Gd(1)-O(4B)#3 2.401(5)

Gd(1)-O(3B) 2.440(5)

Gd(1)-O(4B) 2.589(5)

Gd(2)-O(4)#4 2.303(5)

Gd(2)-O(1A) 2.340(5)

Gd(2)-O(1B)#2 2.347(5)

Gd(2)-O(2) 2.352(5)

Gd(2)-O(3)#5 2.382(5)

Gd(2)-O(2B)#6 2.386(5)

Gd(2)-O(6) 2.450(6)

Gd(2)-O(7) 2.645(6)

Gd(1)-Gd(1)#3 3.9472(8)

S(1)-C(5) 1.718(8)

S(1)-C(2) 1.724(8)

S(1A)-C(5A) 1.722(8)

S(1A)-C(2A) 1.720(8)

S(1B)-C(2B) 1.708(8)

S(1B)-C(5B) 1.724(8)

O(1)-C(1) 1.265(9)

O(2)-C(1) 1.243(9)

O(3)-C(6) 1.256(9)

O(4)-C(6) 1.257(9)

O(1A)-C(1A) 1.262(9)

O(2A)-C(1A) 1.244(9)

O(3A)-C(6A) 1.244(9)

O(4A)-C(6A) 1.285(9)

O(1B)-C(1B) 1.253(9)

O(2B)-C(1B) 1.256(9)

O(3B)-C(6B) 1.240(9)

O(4B)-C(6B) 1.301(9)

C(1)-C(2) 1.482(10)

C(2)-C(3) 1.333(11)

C(3)-C(4) 1.412(11)

C(4)-C(5) 1.355(11)

C(5)-C(6) 1.484(10)

C(1A)-C(2A) 1.501(10)

C(2A)-C(3A) 1.350(11)

C(3A)-C(4A) 1.414(11)

C(4A)-C(5A) 1.361(11)

C(5A)-C(6A) 1.475(10)

C(1B)-C(2B) 1.495(10)

C(2B)-C(3B) 1.352(11)

C(3B)-C(4B) 1.403(11)

C(4B)-C(5B) 1.348(11)

C(5B)-C(6B) 1.474(10)

O(5)-C(7) 1.212(11)

O(6)-C(10) 1.206(11)

N(1)-C(7) 1.299(12)

N(2)-C(10) 1.282(13)

N(1)-C(9) 1.472(13)

N(1)-C(8) 1.486(14)

N(2)-C(12) 1.466(13)

N(2)-C(11) 1.505(14)

O(7)-H(71) 0.89(10)

O(1)-Gd(1)-O(2A) 84.33(19)

O(1)-Gd(1)-O(3A)#1 105.48(19)

O(2A)-Gd(1)-O(3A)#1 145.0(2)

O(1)-Gd(1)-O(4A)#2 92.65(19)

O(2A)-Gd(1)-O(4A)#2 73.9(2)

O(3A)#1-Gd(1)-O(4A)#2 137.12(19)

O(1)-Gd(1)-O(5) 77.27(19)

O(2A)-Gd(1)-O(5) 73.7(2)

O(3A)#1-Gd(1)-O(5) 75.84(19)

163

O(4A)#2-Gd(1)-O(5) 146.88(19)

O(1)-Gd(1)-O(4B)#3 82.00(18)

O(2A)-Gd(1)-O(4B)#3 144.32(19)

O(3A)#1-Gd(1)-O(4B)#3 70.67(18)

O(4A)#2-Gd(1)-O(4B)#3 73.98(19)

O(5)-Gd(1)-O(4B)#3 133.83(18)

O(1)-Gd(1)-O(3B) 151.90(18)

O(2A)-Gd(1)-O(3B) 74.19(19)

O(3A)#1-Gd(1)-O(3B) 83.61(19)

O(4A)#2-Gd(1)-O(3B) 98.4(2)

O(5)-Gd(1)-O(3B) 79.44(19)

O(4B)#3-Gd(1)-O(3B) 125.86(17)

O(1)-Gd(1)-O(4B) 155.55(17)

O(2A)-Gd(1)-O(4B) 108.65(18)

O(3A)#1-Gd(1)-O(4B) 76.09(18)

O(4A)#2-Gd(1)-O(4B) 72.18(18)

O(5)-Gd(1)-O(4B) 125.70(18)

O(4B)#3-Gd(1)-O(4B) 75.49(17)

O(3B)-Gd(1)-O(4B) 51.99(16)

O(4)#4-Gd(2)-O(1A) 140.21(19)

O(4)#4-Gd(2)-O(1B)#2 77.34(19)

O(1A)-Gd(2)-O(1B)#2 78.41(19)

O(4)#4-Gd(2)-O(2) 81.8(2)

O(1A)-Gd(2)-O(2) 98.7(2)

O(1B)#2-Gd(2)-O(2) 141.5(2)

O(4)#4-Gd(2)-O(3)#5 121.1(2)

O(1A)-Gd(2)-O(3)#5 81.80(19)

O(1B)#2-Gd(2)-O(3)#5 75.38(19)

O(2)-Gd(2)-O(3)#5 142.8(2)

O(4)#4-Gd(2)-O(2B)#6 74.74(19)

O(1A)-Gd(2)-O(2B)#6 144.78(18)

O(1B)#2-Gd(2)-O(2B)#6 124.56(18)

O(2)-Gd(2)-O(2B)#6 79.18(19)

O(3)#5-Gd(2)-O(2B)#6 79.71(18)

O(4)#4-Gd(2)-O(6) 144.1(2)

O(1A)-Gd(2)-O(6) 70.91(19)

O(1B)#2-Gd(2)-O(6) 136.8(2)

O(2)-Gd(2)-O(6) 74.2(2)

O(3)#5-Gd(2)-O(6) 70.9(2)

O(2B)#6-Gd(2)-O(6) 74.78(19)

O(4)#4-Gd(2)-O(7) 75.1(2)

O(1A)-Gd(2)-O(7) 67.72(19)

O(1B)#2-Gd(2)-O(7) 72.5(2)

O(2)-Gd(2)-O(7) 71.1(2)

O(3)#5-Gd(2)-O(7) 139.2(2)

O(2B)#6-Gd(2)-O(7) 140.04(19)

O(6)-Gd(2)-O(7) 119.8(2)

164

Table A2-3. Hydrogen coordinates ( x 104) and isotropic displacement parameters

(Å2x 103) for Gd2(C6H2O4S)3(OCHNMe2)2(H2O)

________________________________________________________________________

x y z U(eq)

________________________________________________________________________

H(3A) 2063 2620 2204 39

H(4A) 2746 1476 3387 38

H(3AA) 3239 1721 -1827 38

H(4AA) 2659 787 -3119 36

H(3BA) 5876 3763 -3255 32

H(4BA) 5815 4581 -1979 32

H(7A) 3817 882 -295 63

H(8A) 3741 477 1593 116

H(8B) 3629 -993 1528 116

H(8C) 2883 -99 1243 116

H(9A) 3615 -1227 -445 121

H(9B) 2895 -1557 -79 121

H(9C) 3769 -1991 353 121

H(10A) 1330 1193 596 54

H(11A) 1849 236 -1112 136

H(11B) 914 398 -1418 136

H(11C) 1287 -951 -1216 136

H(12A) 1148 -891 694 127

H(12B) 1444 -1724 78 127

H(12C) 542 -1298 -105 127

H(71) 2500(60) 5520(90) 250(60) 44

________________________________________________________________________

165

Table A2-4: Hydrogen bonds for Gd2(C6H2O4S)3(OCHNMe2)2(H2O)

________________________________________________________________________


________________________________________________________________________

O(7)-H(71)...O(1) 0.89(10) 2.29(10) 3.172(9) 175(9)

O(7)-H(71)...O(2) 0.89(10) 2.30(10) 2.915(9) 126(8)

________________________________________________________________________

Figure A2-1: The perspective drawing of Gd2(C6H2O4S)3(OCHNMe2)2(H2O) with non-

hydrogen atoms represented by thermal ellipsoids drawn to encompass 50% of the electron density

166

(a) (b) Figure A2-2: Perspective drawings of Gd2(C6H2O4S)3(OCHNMe2)2(H2O) down the (a) b-

axis of the unit cell and (b) the a-axis of the unit cell.

167

APPENDIX A3: CRYSTAL STRUCTURE TABLES AND FIGURES FOR

COMPOUND (3) [Eu4(C6H2O4S)6(H2O)2(DMF)3 . (H2O/n-prOH)]

Wake Forest University X-Ray Code: a20n

Table A4-1 Crystal Data and Structure refinement for Eu4(C6H2O4S)6(H2O)2(DMF)3 . (H2O/n-prOH)

Empirical formula C46.50 H42 Eu4 N3 O30 S6





Space group Pc (No. 7)


b = 10.8402(15) Å, β = 90.140(2)°

c = 16.749(2) Å

Volume 3232.1(8) Å3

Z 2



F(000) 1860


Index ranges -21≤h≤21, -13≤k≤13, -20≤l≤20

Reflections collected 26925











________________________________________________________________________

168

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters

(Å2x 103) for Eu4(C6H2O4S)6(OH2)2(DMF)3- (H2O/n-prOH). U(eq) is defined as one

third of the trace of the orthogonalized Uij tensor.

________________________________________________________________________

x y z U(eq)

________________________________________________________________________

Eu(1) 6405(1) 6049(1) -1623(1) 11(1)

Eu(2) 6420(1) 4074(1) -3786(1) 11(1)

Eu(3) 1354(1) 1443(1) -264(1) 12(1)

Eu(4) 1432(1) -355(1) 1880(1) 15(1)

S(1) -1072(2) 3253(4) 1030(3) 18(1)

O(11) -2882(6) 4032(11) 2213(6) 17(3)

O(12) -2533(7) 4582(11) 1002(6) 19(3)

O(13) 648(6) 1381(12) 1781(7) 21(3)

O(14) 394(6) 2160(10) 554(6) 16(3)

C(11) -1712(7) 3315(15) 1777(8) 29(4)

C(12) -1498(8) 2662(14) 2426(8) 24(4)

C(13) -772(8) 2099(15) 2319(8) 28(4)

C(14) -485(6) 2384(13) 1594(7) 12(3)

C(15) -2419(7) 4040(14) 1652(8) 10(4)

C(16) 250(6) 1955(14) 1278(7) 11(3)

S(2) -1041(2) -1578(4) -562(3) 22(1)

O(21) 734(6) -484(10) 638(6) 18(3)

O(22) 383(5) -96(11) -597(6) 14(2)

O(23) -2802(6) -3029(11) 347(7) 20(3)

O(24) -2465(6) -3315(12) -917(6) 20(3)

C(21) -361(7) -1504(13) 157(8) 16(3)

C(22) -516(7) -2227(13) 793(8) 20(4)

C(23) -1214(7) -2874(14) 689(8) 21(4)

C(24) -1550(6) -2606(13) -4(8) 20(4)

C(25) 295(8) -626(16) 60(8) 21(5)

C(26) -2328(6) -3007(16) -204(8) 12(4)

S(3) 3806(2) -2253(5) 420(3) 24(1)

O(31) 5313(7) -3507(12) 464(7) 23(3)

O(32) 5665(5) -2861(10) -738(6) 13(3)

O(33) 2366(6) -1052(10) 867(6) 19(3)

169

O(34) 2079(6) -373(10) -362(7) 25(3)

C(31) 4458(6) -2353(12) -321(7) 11(3)

C(32) 4221(7) -1806(15) -1011(8) 26(4)

C(33) 3496(7) -1247(14) -922(8) 22(4)

C(34) 3221(6) -1408(13) -184(8) 21(3)

C(35) 5206(7) -2953(17) -180(8) 17(4)

C(36) 2497(7) -918(16) 135(8) 18(4)

S(4) 3989(2) 2246(4) 1983(3) 25(1)

O(41) 5491(7) 3238(10) 2388(6) 16(3)

O(42) 5725(6) 4055(9) 1185(7) 13(3)

O(43) 2531(7) 964(11) 2045(7) 26(4)

O(44) 2100(6) 1543(12) 857(7) 26(3)

C(41) 4558(7) 3117(15) 1396(8) 21(4)

C(42) 4241(8) 3400(16) 686(9) 26(4)

C(43) 3529(8) 2797(16) 591(9) 32(5)

C(44) 3324(6) 2176(14) 1243(8) 18(4)

C(45) 5321(7) 3505(14) 1687(7) 9(3)

C(46) 2599(7) 1536(14) 1392(8) 11(4)

S(5) 3882(2) 3350(4) -1440(3) 19(1)

O(51) 2438(6) 2044(11) -1005(7) 18(3)

O(52) 2234(7) 1244(13) -2195(8) 30(4)

O(53) 5324(7) 4666(11) -1388(6) 19(3)

O(54) 5736(6) 4134(10) -2603(7) 15(3)

C(51) 3396(6) 2235(13) -1971(8) 13(3)

C(52) 3771(8) 1820(13) -2618(8) 19(4)

C(53) 4482(8) 2414(13) -2688(9) 24(4)

C(54) 4590(6) 3292(12) -2127(7) 6(3)

C(55) 2622(7) 1824(15) -1707(8) 17(4)

C(56) 5275(8) 4066(15) -2030(8) 19(4)

S(6) -1226(2) 2220(5) -2375(3) 26(1)

O(61) 774(5) 2027(11) -1433(7) 20(3)

O(62) 293(7) 1035(12) -2482(7) 23(3)

O(63) -2912(6) 4175(11) -1579(7) 19(3)

O(64) -2683(6) 3363(11) -2798(6) 22(3)

C(61) -501(6) 2326(14) -1712(7) 13(4)

C(62) -674(9) 3008(17) -1061(9) 38(5)

170

C(63) -1427(9) 3463(19) -1103(10) 42(6)

C(64) -1768(7) 3168(14) -1789(8) 16(4)

C(65) 247(7) 1748(16) -1900(10) 25(5)

C(66) -2525(7) 3582(16) -2076(8) 16(4)

O(1) 6641(7) 8195(12) -1855(7) 29(3)

N(1) 6440(14) 10216(15) -1514(9) 46(4)

C(1) 6288(18) 9110(20) -1769(12) 55(7)

C(2) 5990(15) 11230(30) -1414(18) 77(8)

C(3) 7186(15) 10370(30) -1275(17) 88(10)

O(2) 6179(6) 1874(11) -3626(7) 26(3)

N(2) 6384(15) -110(15) -3829(9) 53(4)

C(4) 6617(9) 1001(16) -3676(10) 21(4)

C(5) 6969(13) -1060(20) -3832(16) 63(7)

C(6) 5650(20) -310(40) -3980(30) 144(17)

O(3) 1225(7) -2555(11) 1682(7) 34(3)

N(3) 1602(14) -4590(20) 1776(13) 79(8)

C(7) 1756(14) -3310(20) 1653(13) 60(7)

C(8) 760(30) -5000(60) 1950(30) 200(30)

C(9) 2215(18) -5410(30) 1690(20) 108(12)

O(4) d 1486(11) 3694(9) -190(11) 47(3)

C(17) d 1139(15) 4420(20) -491(18) 14(7)

C(18) d 1523(18) 5610(20) -652(16) 18(7)

C(19) d 2100(40) 6050(70) -100(40) 150(30)

O(5) 6410(8) 4855(7) -163(6) 21(2)

O(6) 1360(9) 811(8) 3104(6) 23(2)

171

Table 3. Bond lengths [Å] and angles [°] for Eu4(C6H2O4S)6(OH2)2(DMF)3- (H2O/n-

prOH)

________________________________________________________________________

Eu(1)-O(32)#1 2.311(10)

Eu(1)-O(11)#2 2.330(10)

Eu(1)-O(63)#3 2.368(11)

Eu(1)-O(1) 2.396(13)

Eu(1)-O(24)#4 2.431(10)

Eu(1)-O(41)#5 2.444(10)

Eu(1)-O(53) 2.472(12)

Eu(1)-O(5) 2.767(10)

Eu(1)-O(54) 2.900(11)

Eu(2)-O(23)#6 2.306(10)

Eu(2)-O(54) 2.331(10)

Eu(2)-O(42)#5 2.377(10)

Eu(2)-O(12)#2 2.393(11)

Eu(2)-O(31)#7 2.414(11)

Eu(2)-O(64)#3 2.422(11)

Eu(2)-O(2) 2.438(12)

Eu(2)-O(5)#5 2.581(9)

Eu(2)-O(11)#2 2.924(11)

Eu(1)-Eu(2) 4.2091(9) Eu(3)-Eu(4) 4.0889(11)

Eu(3)-O(44) 2.300(11)

Eu(3)-O(61) 2.300(11)

Eu(3)-O(14) 2.327(10)

Eu(3)-O(34) 2.359(10)

Eu(3)-O(51) 2.387(10)

Eu(3)-O(22) 2.465(11)

Eu(3)-O(4) 2.455(10)

Eu(3)-O(21) 2.805(11)

Eu(4)-O(52)#8 2.315(11)

Eu(4)-O(13) 2.349(11)

Eu(4)-O(6) 2.412(10)

Eu(4)-O(62)#8 2.410(12)

Eu(4)-O(21) 2.425(10)

Eu(4)-O(3) 2.436(12)

Eu(4)-O(43) 2.439(11)

Eu(4)-O(33) 2.496(10)

Eu(4)-O(44) 2.933(13)

S(1)-C(14) 1.694(11)

S(1)-C(11) 1.695(11)

O(11)-C(15) 1.252(12)

O(11)-Eu(1)#9 2.330(10)

O(11)-Eu(2)#9 2.924(11)

O(12)-C(15) 1.253(12)

O(12)-Eu(2)#9 2.393(11)

O(13)-C(16) 1.263(12)

O(14)-C(16) 1.259(12)

C(11)-C(12) 1.351(14)

C(11)-C(15) 1.499(13)

C(12)-C(13) 1.441(13)

S(2)-C(21) 1.708(11)

S(2)-C(24) 1.714(11)

O(21)-C(25) 1.252(13)

O(22)-C(25) 1.252(13)

O(23)-C(26) 1.253(13)

O(23)-Eu(2)#10 2.306(10)

O(24)-C(26) 1.263(13)

O(24)-Eu(1)#11 2.431(10)

C(21)-C(22) 1.351(13)

C(21)-C(25) 1.515(13)

C(22)-C(23) 1.438(13)

C(23)-C(24) 1.338(14)

O(21)-C(25) 1.252(13)

O(22)-C(25) 1.252(13)

O(23)-C(26) 1.253(13)

O(23)-Eu(2)#10 2.306(10)

O(24)-C(26) 1.263(13)

172

O(24)-Eu(1)#11 2.431(10)

C(21)-C(22) 1.351(13)

C(21)-C(25) 1.515(13)

C(22)-C(23) 1.438(13)

C(23)-C(24) 1.338(14)

O(32)#1-Eu(1)-O(11)#2 150.3(4)

O(32)#1-Eu(1)-O(63)#3 135.4(4)

O(11)#2-Eu(1)-O(63)#3 73.3(4)

O(32)#1-Eu(1)-O(1) 73.0(4)

O(11)#2-Eu(1)-O(1) 78.8(4)

O(63)#3-Eu(1)-O(1) 138.4(4)

O(32)#1-Eu(1)-O(24)#4 90.9(4)

O(11)#2-Eu(1)-O(24)#4 88.1(4)

O(63)#3-Eu(1)-O(24)#4 78.7(4)

O(1)-Eu(1)-O(24)#4 70.0(4)

O(32)#1-Eu(1)-O(41)#5 83.9(4)

O(11)#2-Eu(1)-O(41)#5 78.9(4)

O(63)#3-Eu(1)-O(41)#5 129.3(4)

O(1)-Eu(1)-O(41)#5 72.5(4)

O(24)#4-Eu(1)-O(41)#5 142.0(4)

O(32)#1-Eu(1)-O(53) 76.3(4)

O(11)#2-Eu(1)-O(53) 122.4(4)

O(63)#3-Eu(1)-O(53) 82.8(4)

O(1)-Eu(1)-O(53) 138.7(4)

O(24)#4-Eu(1)-O(53) 137.6(4)

O(41)#5-Eu(1)-O(53) 77.4(4)

O(32)#1-Eu(1)-O(5) 70.9(3)

O(11)#2-Eu(1)-O(5) 136.2(4)

O(63)#3-Eu(1)-O(5) 64.6(4)

O(1)-Eu(1)-O(5) 126.7(3)

O(24)#4-Eu(1)-O(5) 72.7(4)

O(41)#5-Eu(1)-O(5) 138.4(4)

O(53)-Eu(1)-O(5) 64.9(4)

O(32)#1-Eu(1)-O(54) 119.7(3)

O(11)#2-Eu(1)-O(54) 73.9(3)

O(63)#3-Eu(1)-O(54) 67.3(4)

O(1)-Eu(1)-O(54) 132.4(4)

O(24)#4-Eu(1)-O(54) 144.8(4)

O(41)#5-Eu(1)-O(54) 64.6(3)

O(53)-Eu(1)-O(54) 48.5(3)

O(5)-Eu(1)-O(54) 99.5(3)

O(32)#1-Eu(1)-Eu(2) 144.8(3)

O(11)#2-Eu(1)-Eu(2) 41.9(3)

O(63)#3-Eu(1)-Eu(2) 65.5(3)

O(1)-Eu(1)-Eu(2) 110.6(3)

O(24)#4-Eu(1)-Eu(2) 123.8(2)

O(41)#5-Eu(1)-Eu(2) 65.3(3)

O(53)-Eu(1)-Eu(2) 80.5(2)

O(5)-Eu(1)-Eu(2) 121.55(15)

O(54)-Eu(1)-Eu(2) 32.0(2)

O(23)#6-Eu(2)-O(54) 149.9(4)

O(23)#6-Eu(2)-O(42)#5 136.1(4)

O(54)-Eu(2)-O(42)#5 73.7(4)

O(23)#6-Eu(2)-O(12)#2 74.7(4)

O(54)-Eu(2)-O(12)#2 121.2(4)

O(42)#5-Eu(2)-O(12)#2 83.3(4)

O(23)#6-Eu(2)-O(31)#7 92.2(5)

O(54)-Eu(2)-O(31)#7 91.3(4)

O(42)#5-Eu(2)-O(31)#7 77.5(4)

O(12)#2-Eu(2)-O(31)#7 135.5(4)

O(23)#6-Eu(2)-O(64)#3 83.0(4)

O(54)-Eu(2)-O(64)#3 76.9(4)

O(42)#5-Eu(2)-O(64)#3 128.9(4)

O(12)#2-Eu(2)-O(64)#3 77.4(4)

O(31)#7-Eu(2)-O(64)#3 144.1(4)

O(23)#6-Eu(2)-O(2) 72.3(4)

O(54)-Eu(2)-O(2) 80.9(4)

173

Table 7. Hydrogen bonds for Eu4(C6H2O4S)6(OH2)2(DMF)3- (H2O/n-prOH [Å and °].

________________________________________________________________________


________________________________________________________________________

O(6)-H(6)...O(34)#8 0.847(10) 2.24(12) 2.906(17) 136(15)

________________________________________________________________________

Figure A3-1: A perspective drawing of the contents of the asymmetric unit for Eu4(C6H2O4S)6(OH2)2(DMF)3- (H2O/n-prOH) . Europium and sulfur atoms are represented by large cross-hatched or dotted spheres, oxygen and nitrogen atoms are represented by medium-sized shaded spheres and carbon and hydrogen atoms are represented by medium and small open spheres, respectively.

174

Figure A3-2: A perspective drawing of Eu4(C6H2O4S)6(OH2)2(DMF)3- (H2O/n-prOH with completed coordination spheres for each of the europium atoms. Europium and sulfur atoms are represented by 50% probability ellipsoids and the remaining atoms are represented as described in Figure A3-1. Hydrogen atoms have been omitted from this view for purposes of clarity.

Figures A3-3: A projection of the unit cell when viewed down the c-axis in crystalline

Eu4(C6H2O4S)6(OH2)2(DMF)3- (H2O/n-prOH) with atoms represented as in Figure A3-1. Hydrogen atoms have been omitted from these views for purposes of clarity.

175

APPENDIX A4: CRYSTAL STRUCTURE TABLES AND FIGURES FOR COMPOUND (4) [Y(C6H2O4S)(NO3)(ONC3H7)2]

Wake Forest University X-Ray Code: a23m

Table A4-1 Crystal Data and Structure refinement for Y(C6H2O4S)(NO3)(ONC3H7)2

________________________________________________________________________

Identification code a77l2m

Empirical formula C12 H16 N3 O9 S Y





Space group P2(1)/n


b = 10.668(4) Å, β = 95.870(6)°

c = 15.709(5) Å

Volume 1768.3(10) Å3

Z 4



F(000) 944



Index ranges -13≤h≤13, -13≤k≤12, -19≤l≤19






Data / parameters 3590 / 307




Largest diff. peak and hole 0.487 and -0.649 e.Å-3

_______________________________________________________________________

176

Table A4-2. Atomic coordinates ( x 104) and equivalent isotropic displacement

parameters (Å2x 103) for Y(C6H2O4S)(NO3)(ONC3H7)2. U(eq) is defined as one third of

the trace of the orthogonalized Uij tensor.

________________________________________________________________________

x y z U(eq)

________________________________________________________________________

Y(1) 2509(1) 4678(1) 182(1) 19(1)

S(1) 4393(2) 7332(2) 2504(1) 27(1)

O(1) 4132(4) 5373(5) 1168(3) 38(1)

O(2) 5915(4) 9661(5) 4228(3) 46(1)

O(3) 3107(5) 6856(4) -176(3) 47(1)

O(4) 1843(5) 6662(4) 787(3) 45(1)

O(5) 2512(6) 8515(5) 475(4) 76(2)

O(6) 1601(5) 2889(5) -554(4) 54(2)

O(7) 3419(5) 2888(5) 814(3) 50(1)

O(8) 6097(4) 5524(4) 794(3) 36(1)

O(9) 3907(4) 9098(4) 3890(3) 32(1)

N(1) 4520(14) 1337(14) 1468(12) 32(4)

N(2) 528(15) 1098(14) -911(11) 43(4)

N(3) 2481(6) 7376(6) 360(4) 51(2)

C(1) 5223(6) 5798(6) 1246(4) 27(2)

C(2) 5544(6) 6728(6) 1950(4) 32(2)

C(3) 6709(7) 7189(8) 2225(5) 58(3)

C(4) 6666(7) 8054(8) 2886(5) 53(2)

C(5) 5460(6) 8224(6) 3109(4) 33(2)

C(6) 5071(6) 9043(6) 3789(4) 24(1)

C(7) 4256(8) 2216(8) 797(7) 73(3)

C(8) 5732(13) 708(13) 1581(13) 65(6)

C(9) 3490(40) 810(40) 1873(18) 35(6)

C(9') 3850(50) 850(50) 1820(30) 90(20)

C(10) 1187(14) 1938(15) -397(11) 46(4)

C(11) 299(14) -127(12) -629(10) 51(5)

C(12) 40(20) 1460(20) -1781(19) 77(11)

N(1') 4350(19) 1017(18) 1013(10) 43(5)

C(8') 5136(16) 2(14) 774(12) 58(6)

N(2') 613(15) 1450(16) -1398(15) 32(4)

177

C(10') 825(13) 2539(15) -958(9) 30(4)

C(11') 1589(17) 469(15) -1291(11) 59(5)

C(12') -495(19) 1203(19) -1938(13) 34(5)

The nitrogen and carbon atoms of both DMF solvent molecules are disordered over two

preferred orientations and were refined with corresponding occupancies of 52% and 48%,

respectively.

Table A4-3. Bond lengths [Å] and angles [°] for Y(C6H2O4S)(NO3)(ONC3H7)2

______________________________________________________________________

Y(1)-O(8)#1 2.246(4)

Y(1)-O(2)#2 2.254(4)

Y(1)-O(9)#3 2.283(4)

Y(1)-O(7) 2.317(5)

Y(1)-O(1) 2.318(4)

Y(1)-O(6) 2.383(5)

Y(1)-O(4) 2.453(4)

Y(1)-O(3) 2.488(5)

S(1)-C(5) 1.694(6) S(1)-C(2) 1.697(6)

O(1)-C(1) 1.237(7)

O(2)-C(6) 1.259(7)

O(8)-C(1) 1.259(7)

O(9)-C(6) 1.262(7)

O(3)-N(3) 1.254(7)

O(4)-N(3) 1.256(7)

O(5)-N(3) 1.229(7)

O(6)-C(10') 1.055(14)

O(6)-C(10) 1.142(16)

O(7)-C(7) 1.144(8)

N(1)-C(7) 1.417(18)

N(1)-C(9) 1.43(4)

N(1)-C(8) 1.445(19)

N(2)-C(10) 1.35(2)

N(2)-C(11) 1.408(19)

N(2)-C(12) 1.46(3)

C(1)-C(2) 1.499(8)

C(2)-C(3) 1.359(8)

C(3)-C(4) 1.393(9)

C(4)-C(5) 1.372(9)

C(5)-C(6) 1.472(8)

C(7)-N(1') 1.32(2) N(2')-C(10') 1.36(2)

C(9')-N(1') 1.44(4)

N(1')-C(8') 1.44(2)

N(2')-C(12') 1.40(2)

N(2')-C(11') 1.47(2)

O(8)#1-Y(1)-O(2)#2 94.45(16)

O(8)#1-Y(1)-O(9)#3 158.72(16)

O(2)#2-Y(1)-O(9)#3 90.67(16)

O(8)#1-Y(1)-O(7) 86.52(17)

O(2)#2-Y(1)-O(7) 142.58(18)

O(9)#3-Y(1)-O(7) 77.02(17)

O(8)#1-Y(1)-O(1) 89.50(15)

O(2)#2-Y(1)-O(1) 143.07(17)

O(9)#3-Y(1)-O(1) 98.74(15)

O(7)-Y(1)-O(1) 74.26(17)

178

O(8)#1-Y(1)-O(6) 81.59(17)

O(2)#2-Y(1)-O(6) 72.0(2)

O(9)#3-Y(1)-O(6) 80.40(17)

O(7)-Y(1)-O(6) 71.2(2)

O(1)-Y(1)-O(6) 144.7(2)

O(8)#1-Y(1)-O(4) 125.64(17)

O(2)#2-Y(1)-O(4) 76.20(17)

O(9)#3-Y(1)-O(4) 75.64(16)

O(7)-Y(1)-O(4) 131.95(17)

O(1)-Y(1)-O(4) 71.83(16)

O(6)-Y(1)-O(4) 139.54(19)

O(8)#1-Y(1)-O(3) 74.62(16)

O(2)#2-Y(1)-O(3) 75.44(17)

O(9)#3-Y(1)-O(3) 126.63(16)

O(7)-Y(1)-O(3) 139.63(18)

O(1)-Y(1)-O(3) 70.30(16)

O(6)-Y(1)-O(3) 137.58(19)

O(4)-Y(1)-O(3) 51.09(16)

C(5)-S(1)-C(2) 91.5(3)

C(1)-O(1)-Y(1) 143.8(4)

C(6)-O(2)-Y(1)#4 166.1(5)

N(3)-O(3)-Y(1) 95.5(4)

N(3)-O(4)-Y(1) 97.2(4)

C(10')-O(6)-Y(1) 145.8(11)

C(10)-O(6)-Y(1) 138.8(10)

C(7)-O(7)-Y(1) 142.8(6)

C(1)-O(8)-Y(1)#1 169.0(4)

C(6)-O(9)-Y(1)#5 144.0(4)

C(7)-N(1)-C(9) 119(2)

C(7)-N(1)-C(8) 120.3(15)

C(9)-N(1)-C(8) 118(2)

C(10)-N(2)-C(11) 121.6(15)

C(10)-N(2)-C(12) 119.4(17)

C(11)-N(2)-C(12) 119.0(15)

179

Figure A4-1: A view of the asymmetric unit of Y(C6H2O4S)(NO3)(ONC3H7)2 with nonhydrogen and hydrogen atoms represented by arbitrarily small spheres, which are in no way representative of their true thermal motion.

180

Figure A4-2: A view of the framework of Y(C6H2O4S)(NO3)(ONC3H7)2 projected down the a-axis with nonhydrogen atoms represented by arbitrarily small spheres, which are in no way representative of their true thermal motion. Hydrogen atoms omitted for clarity.

181

Figure A4-3: A view of the framework of Y(C6H2O4S)(NO3)(ONC3H7)2 projected down the b-axis with nonhydrogen atoms represented by arbitrarily small spheres, which are in no way representative of their true thermal motion. Hydrogen atoms omitted for clarity.

182

APPENDIX A5: CRYSTAL STRUCTURE TABLES AND FIGURES FOR COMPOUND (5) [Tb2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)]

Wake Forest University X-Ray Code: a36o

Table A5-1 Crystal Data and Structure refinement for Tb2(C8O4F4)3(EtOH)2(Et2NCHO)2

- 2(Et2NCHO)

________________________________________________________________________

Identification code a36o2m

Empirical formula C48 H56 F12 N4 O18 Tb2




Crystal system Monoclinic Space group C2/c – C 6

2h (No. 15)


b = 11.185(2) Å, β = 108.650(2)°

c = 23.230(3) Å

Volume 5731.6(13) Å3

Z 4



F(000) 3016



Index ranges -32≤h≤32, -15≤k≤15, -32≤l≤30








Final R indices [6637 I>2σ(I)] R1 = 0.0412, wR2 = 0.0829



________________________________________________________________________

183

Table A5-2. Bond lengths [Å] and angles [°] for Tb2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)

a,b

________________________________________________________________________

Tb(1)-O(1) 2.366(2)

Tb(1)-O(2)#1 2.319(2)

Tb(1)-O(3) 2.469(2)

Tb(1)-O(4) 2.457(3)

Tb(1)-O(5)#3 2.478(3)

Tb(1)-O(6)#3 2.747(3)

Tb(1)-O(6)#2 2.349(3)

Tb(1)-O(7) 2.381(2)

Tb(1)-O(8) 2.409(3)

F(1)-C(3) 1.351(4)

F(2)-C(4) 1.339(4)

F(3)-C(9) 1.337(4)

F(4)-C(10) 1.346(4)

F(5)-C(12) 1.337(4)

F(6)-C(13) 1.335(4)

O(1)-C(1) 1.249(3)

O(2)-C(6) 1.247(3)

O(3)-C(7) 1.246(4)

O(4)-C(7) 1.259(4)

O(5)-C(14) 1.239(5)

O(6)-C(14) 1.255(4)

C(1)-C(2) 1.507(7)

C(5)-C(6) 1.497(6)

C(7)-C(8) 1.512(5)

C(11)-C(14) 1.513(5)

C(2)-C(3) 1.383(4)

C(3)-C(4) 1.374(5)

C(4)-C(5) 1.388(4)

C(8)-C(9) 1.400(5)

C(8)-C(13) 1.387(5)

C(9)-C(10) 1.376(5)

C(10)-C(11) 1.374(5)

C(11)-C(12) 1.377(5)

C(12)-C(13) 1.390(5)

O(7)-C(15) 1.229(4)

O(9)-C(22) 1.224(5)

N(1)-C(15) 1.322(5)

N(2)-C(22) 1.335(6)

N(1)-C(16) 1.467(6)

N(1)-C(18) 1.482(5)

N(2)-C(25) 1.461(6)

N(2)-C(23) 1.466(6)

C(16)-C(17) 1.493(7)

C(18)-C(19) 1.508(7)

C(23)-C(24) 1.501(8)

C(25)-C(26) 1.483(7)

O(8)-C(20) 1.448(6)

O(8)-H(8O) 0.87(5)

C(20)-C(21) 1.460(8)

O(2)#1-Tb(1)-O(6)#2 74.77(9)

O(2)#1-Tb(1)-O(1) 131.17(9)

O(6)#2-Tb(1)-O(1) 72.72(8)

O(2)#1-Tb(1)-O(7) 139.38(9)

O(6)#2-Tb(1)-O(7) 145.00(8)

O(1)-Tb(1)-O(7) 75.65(9)

O(2)#1-Tb(1)-O(8) 73.10(10)

O(6)#2-Tb(1)-O(8) 137.93(9)

O(1)-Tb(1)-O(8) 149.14(9)

O(7)-Tb(1)-O(8) 73.90(10)

O(2)#1-Tb(1)-O(4) 130.17(9)

O(6)#2-Tb(1)-O(4) 86.13(9)

O(1)-Tb(1)-O(4) 82.59(9)

O(7)-Tb(1)-O(4) 75.21(9)

O(8)-Tb(1)-O(4) 94.35(10)

O(2)#1-Tb(1)-O(3) 77.54(9)

184

O(6)#2-Tb(1)-O(3) 74.24(9)

O(1)-Tb(1)-O(3) 125.39(9)

O(7)-Tb(1)-O(3) 114.06(9)

O(8)-Tb(1)-O(3) 72.89(9)

O(4)-Tb(1)-O(3) 52.89(9)

O(2)#1-Tb(1)-O(5)#3 78.25(9)

O(6)#2-Tb(1)-O(5)#3 120.29(9)

O(1)-Tb(1)-O(5)#3 87.83(9)

O(7)-Tb(1)-O(5)#3 72.51(9)

O(8)-Tb(1)-O(5)#3 78.45(10)

O(4)-Tb(1)-O(5)#3 147.68(9)

O(3)-Tb(1)-O(5)#3 146.72(9)

O(2)#1-Tb(1)-O(6)#3 68.86(8)

O(6)#2-Tb(1)-O(6)#3 71.32(9)

O(1)-Tb(1)-O(6)#3 66.75(8)

O(7)-Tb(1)-O(6)#3 109.15(8)

O(8)-Tb(1)-O(6)#3 119.53(9)

O(4)-Tb(1)-O(6)#3 145.95(9)

O(3)-Tb(1)-O(6)#3 136.76(8)

O(5)#3-Tb(1)-O(6)#3 49.33(8)

C(1)-O(1)-Tb(1) 138.6(3)

C(6)-O(2)-Tb(1)#4 139.2(3)

C(7)-O(3)-Tb(1) 92.3(2)

C(7)-O(4)-Tb(1) 92.5(2)

C(14)-O(5)-Tb(1)#5 100.3(2)

C(14)-O(6)-Tb(1)#2 161.0(2)

C(14)-O(6)-Tb(1)#5 87.1(2)

Tb(1)#2-O(6)-Tb(1)#5 108.61(9)

O(1)-C(1)-O(1)#6 128.4(5)

O(1)-C(1)-C(2) 115.8(2)

O(1)#6-C(1)-C(2) 115.8(2)

C(3)#6-C(2)-C(3) 116.5(5)

C(3)#6-C(2)-C(1) 121.8(2)

C(3)-C(2)-C(1) 121.8(2)

F(1)-C(3)-C(4) 117.6(3)

F(1)-C(3)-C(2) 120.3(3)

C(4)-C(3)-C(2) 122.0(3)

F(2)-C(4)-C(3) 118.7(3)

F(2)-C(4)-C(5) 119.8(3)

C(3)-C(4)-C(5) 121.5(3)

C(4)-C(5)-C(4)#6 116.6(4)

C(4)-C(5)-C(6) 121.7(2)

C(4)#6-C(5)-C(6) 121.7(2)

O(2)-C(6)-O(2)#6 128.6(5)

O(2)-C(6)-C(5) 115.7(2)

O(2)#6-C(6)-C(5) 115.7(2)

O(3)-C(7)-O(4) 122.3(3)

O(3)-C(7)-C(8) 118.1(3)

O(4)-C(7)-C(8) 119.6(3)

C(13)-C(8)-C(9) 116.0(3)

C(13)-C(8)-C(7) 122.9(3)

C(9)-C(8)-C(7) 121.1(3)

F(3)-C(9)-C(10) 117.7(3)

F(3)-C(9)-C(8) 121.0(3)

C(10)-C(9)-C(8) 121.3(3)

F(4)-C(10)-C(11) 119.1(3)

F(4)-C(10)-C(9) 118.6(3)

C(11)-C(10)-C(9) 122.3(4)

C(10)-C(11)-C(12) 117.2(3)

C(10)-C(11)-C(14) 120.6(3)

C(12)-C(11)-C(14) 122.2(3)

F(5)-C(12)-C(11) 120.0(3)

F(5)-C(12)-C(13) 118.8(3)

C(11)-C(12)-C(13) 121.2(3)

F(6)-C(13)-C(8) 120.7(3)

F(6)-C(13)-C(12) 117.2(3)

C(8)-C(13)-C(12) 122.0(3)

O(5)-C(14)-O(6) 123.3(3)

O(5)-C(14)-C(11) 118.5(3)

O(6)-C(14)-C(11) 118.2(3)

185

Table A5-3. Torsion angles [°] for Tb2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)

________________________________________________________________________

O(2)#1-Tb(1)-O(1)-C(1) 22.5(3)

O(6)#2-Tb(1)-O(1)-C(1) -27.9(2)

O(7)-Tb(1)-O(1)-C(1) 167.3(3)

O(8)-Tb(1)-O(1)-C(1) 157.8(2)

O(4)-Tb(1)-O(1)-C(1) -116.1(3)

O(3)-Tb(1)-O(1)-C(1) -83.1(3)

O(5)#3-Tb(1)-O(1)-C(1) 94.8(3)

O(6)#3-Tb(1)-O(1)-C(1) 48.7(2)

O(2)#1-Tb(1)-O(3)-C(7) -174.3(2)

O(6)#2-Tb(1)-O(3)-C(7) -96.9(2)

O(1)-Tb(1)-O(3)-C(7) -42.2(3)

O(7)-Tb(1)-O(3)-C(7) 46.9(2)

O(8)-Tb(1)-O(3)-C(7) 109.8(2)

O(4)-Tb(1)-O(3)-C(7) 0.4(2)

O(5)#3-Tb(1)-O(3)-C(7) 141.5(2)

O(6)#3-Tb(1)-O(3)-C(7) -135.0(2)

C(14)#3-Tb(1)-O(3)-C(7) -172.0(2)

O(2)#1-Tb(1)-O(4)-C(7) 6.5(3)

O(6)#2-Tb(1)-O(4)-C(7) 72.8(2)

O(1)-Tb(1)-O(4)-C(7) 145.8(2)

O(7)-Tb(1)-O(4)-C(7) -137.1(2)

O(8)-Tb(1)-O(4)-C(7) -65.0(2)

O(3)-Tb(1)-O(4)-C(7) -0.4(2)

O(5)#3-Tb(1)-O(4)-C(7) -140.2(2)

O(6)#3-Tb(1)-O(4)-C(7) 120.4(2)

Tb(1)-O(1)-C(1)-O(1)#6 -10.25(18)

Tb(1)-O(1)-C(1)-C(2) 169.75(18)

O(1)-C(1)-C(2)-C(3)#6 48.0(2)

O(1)#6-C(1)-C(2)-C(3)#6 -132.0(2)

O(1)-C(1)-C(2)-C(3) -132.0(2)

O(1)#6-C(1)-C(2)-C(3) 48.0(2)

C(3)#6-C(2)-C(3)-F(1) -176.7(4)

C(1)-C(2)-C(3)-F(1) 3.2(4)

C(3)#6-C(2)-C(3)-C(4) -0.2(2)

186

C(1)-C(2)-C(3)-C(4) 179.8(2)

F(1)-C(3)-C(4)-F(2) -0.3(5)

C(2)-C(3)-C(4)-F(2) -176.9(3)

F(1)-C(3)-C(4)-C(5) 177.1(3)

C(2)-C(3)-C(4)-C(5) 0.5(5)

F(2)-C(4)-C(5)-C(4)#6 177.1(4)

C(3)-C(4)-C(5)-C(4)#6 -0.2(2)

F(2)-C(4)-C(5)-C(6) -2.9(4)

C(3)-C(4)-C(5)-C(6) 179.8(2)

Tb(1)#4-O(2)-C(6)-O(2)#6 9.45(18)

Tb(1)#4-O(2)-C(6)-C(5) -170.54(18)

C(4)-C(5)-C(6)-O(2) 130.9(2)

C(4)#6-C(5)-C(6)-O(2) -49.1(2)

C(4)-C(5)-C(6)-O(2)#6 -49.1(2)

C(4)#6-C(5)-C(6)-O(2)#6 130.9(2)

Tb(1)-O(3)-C(7)-O(4) -0.7(4)

Tb(1)-O(3)-C(7)-C(8) 179.5(3)

Tb(1)-O(4)-C(7)-O(3) 0.7(4)

Tb(1)-O(4)-C(7)-C(8) -179.5(3)

O(3)-C(7)-C(8)-C(13) -150.4(4)

O(4)-C(7)-C(8)-C(13) 29.7(6)

O(3)-C(7)-C(8)-C(9) 28.5(5)

O(4)-C(7)-C(8)-C(9) -151.3(4)

C(13)-C(8)-C(9)-F(3) -179.9(4)

C(7)-C(8)-C(9)-F(3) 1.1(6)

C(13)-C(8)-C(9)-C(10) 0.6(6)

C(7)-C(8)-C(9)-C(10) -178.4(4)

F(3)-C(9)-C(10)-F(4) 1.1(6)

C(8)-C(9)-C(10)-F(4) -179.4(4)

F(3)-C(9)-C(10)-C(11) -179.2(4)

C(8)-C(9)-C(10)-C(11) 0.3(6)

________________________________________________________________

187

Table A5-4. Hydrogen bonds for Tb2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) [Å

and °]

________________________________________________________________________


________________________________________________________________________

O(8)-H(8O)...O(9) 0.87(5) 1.87(5) 2.699(4) 159(4)

________________________________________________________________________

Figure A5-1: shows a perspective drawing of the contents of the asymmetric unit for Tb2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO). Nonhydrogen atoms are represented by thermal vibration ellipsoids drawn to encompass 50% of their electron density. Hydrogen atoms are represented by arbitrarily-small spheres, which are in no way representative of their true thermal motion.

188

Figure A5-2: Perspective view of projections down the a-axis of the unit cell in crystalline Tb2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) Hydrogen atoms have been omitted for clarity.

189

APPENDIX A6: CRYSTAL STRUCTURE TABLES AND FIGURES FOR COMPOUND (6) [Gd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)]


Table A6-1 Crystal Data and Structure refinement for Gd2(C8O4F4)3(EtOH)2(Et2NCHO)2

- 2(Et2NCHO)

________________________________________________________________________


Empirical formula C48 H56 F12 N4 O18 Gd2





2h (No. 15)


b = 11.2196(15) Å, β = 108.630(2)°

c = 23.249(3) Å

Volume 5762.2(14) Å3

Z 4



F(000) 3008



Index ranges -31≤h≤31, -14≤k≤15, -31≤l≤31








Final R indices [6196 I>2σ(I)] R1 = 0.0472, wR2 = 0.0930


Largest diff. peak and hole 1.678 and -2.168 e-/Å3 _______________________________________________________________________

190

Table A6-2. Bond lengths [Å] and angles [°] for Gd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)

a,b

________________________________________________________________________

Gd(1)-O(2)#1 2.333(3)

Gd(1)-O(6)#2 2.370(3)

Gd(1)-O(1) 2.380(3)

Gd(1)-O(7) 2.401(3)

Gd(1)-O(8) 2.426(3)

Gd(1)-O(4) 2.470(3)

Gd(1)-O(3) 2.489(3)

Gd(1)-O(5)#3 2.490(3)

Gd(1)-O(6)#3 2.726(3)

F(1)-C(3) 1.337(5)

F(2)-C(4) 1.338(5)

F(3)-C(9) 1.343(5)

F(4)-C(10) 1.341(5)

F(5)-C(12) 1.338(5)

F(6)-C(13) 1.342(5)

O(1)-C(1) 1.248(4)

O(2)-C(6) 1.249(4)

O(3)-C(7) 1.248(5)

O(4)-C(7) 1.248(5)

O(5)-C(14) 1.235(6)

O(6)-C(14) 1.252(5)

C(1)-C(2) 1.517(8)

C(5)-C(6) 1.506(8)

C(7)-C(8) 1.506(6)

C(11)-C(14) 1.518(6)

C(2)-C(3) 1.387(5)

C(3)-C(4) 1.384(6)

C(4)-C(5) 1.376(5)

C(8)-C(13) 1.373(6)

C(8)-C(9) 1.406(6)

C(9)-C(10) 1.366(6)

C(10)-C(11) 1.378(6)

C(11)-C(12) 1.381(6)

C(12)-C(13) 1.386(6)

O(7)-C(15) 1.234(5)

O(9)-C(22) 1.235(7)

N(1)-C(15) 1.320(6)

N(2)-C(22) 1.342(7)

N(1)-C(16) 1.467(6)

N(1)-C(18) 1.482(5)

N(2)-C(25) 1.461(6)

N(2)-C(23) 1.466(6)

C(16)-C(17) 1.495(10)

C(18)-C(19) 1.494(10)

C(23)-C(24) 1.490(10)

C(25)-C(26) 1.481(9)

O(8)-C(20) 1.450(8)

O(8)-H(8O) 0.79(6)

C(20)-C(21) 1.455(10)

O(2)#1-Gd(1)-O(6)#2 74.83(11)

O(2)#1-Gd(1)-O(1) 131.78(10)

O(6)#2-Gd(1)-O(1) 72.57(10)

O(2)#1-Gd(1)-O(7) 139.13(11)

O(6)#2-Gd(1)-O(7) 145.17(10)

O(1)-Gd(1)-O(7) 75.70(11)

O(2)#1-Gd(1)-O(8) 73.15(12)

O(6)#2-Gd(1)-O(8) 138.02(11)

O(1)-Gd(1)-O(8) 149.10(12)

O(7)-Gd(1)-O(8) 73.66(12)

O(2)#1-Gd(1)-O(4) 129.80(11)

O(6)#2-Gd(1)-O(4) 86.66(11)

O(1)-Gd(1)-O(4) 82.50(11)

O(7)-Gd(1)-O(4) 75.24(11)

O(8)-Gd(1)-O(4) 93.48(13)

O(2)#1-Gd(1)-O(3) 77.49(11)

191

O(6)#2-Gd(1)-O(3) 74.23(11)

O(1)-Gd(1)-O(3) 124.64(11)

O(7)-Gd(1)-O(3) 114.16(11)

O(8)-Gd(1)-O(3) 72.91(12)

O(4)-Gd(1)-O(3) 52.47(11)

O(2)#1-Gd(1)-O(5)#3 78.25(11)

O(6)#2-Gd(1)-O(5)#3 120.24(11)

O(1)-Gd(1)-O(5)#3 88.57(11)

O(7)-Gd(1)-O(5)#3 72.36(11)

O(8)-Gd(1)-O(5)#3 78.51(12)

O(4)-Gd(1)-O(5)#3 147.59(12)

O(3)-Gd(1)-O(5)#3 146.74(11)

O(2)#1-Gd(1)-O(6)#3 69.33(9)

O(6)#2-Gd(1)-O(6)#3 71.36(11)

O(1)-Gd(1)-O(6)#3 67.12(10)

O(7)-Gd(1)-O(6)#3 108.78(10)

O(8)-Gd(1)-O(6)#3 119.86(11)

O(4)-Gd(1)-O(6)#3 146.46(11)

O(3)-Gd(1)-O(6)#3 137.04(10)

O(5)#3-Gd(1)-O(6)#3 49.29(10)

C(1)-O(1)-Gd(1) 137.9(3)

C(6)-O(2)-Gd(1)#4 139.2(3)

C(7)-O(3)-Gd(1) 91.9(3)

C(7)-O(4)-Gd(1) 92.7(3)

C(14)-O(5)-Gd(1)#5 99.7(3)

C(14)-O(6)-Gd(1)#2 159.8(3)

C(14)-O(6)-Gd(1)#5 88.0(3)

Gd(1)#2-O(6)-Gd(1)#5 108.57(11)

O(1)#6-C(1)-O(1) 129.5(5)

O(1)#6-C(1)-C(2) 115.3(3)

O(1)-C(1)-C(2) 115.3(3)

C(3)#6-C(2)-C(3) 117.1(5)

C(3)#6-C(2)-C(1) 121.5(3)

C(3)-C(2)-C(1) 121.5(3)

F(1)-C(3)-C(4) 118.3(4)

F(1)-C(3)-C(2) 120.3(4)

C(4)-C(3)-C(2) 121.3(4)

F(2)-C(4)-C(5) 120.8(4)

F(2)-C(4)-C(3) 118.0(4)

C(5)-C(4)-C(3) 121.1(4)

C(4)-C(5)-C(4)#6 118.0(6)

C(4)-C(5)-C(6) 121.0(3)

C(4)#6-C(5)-C(6) 121.0(3)

O(2)#6-C(6)-O(2) 128.3(6)

O(2)#6-C(6)-C(5) 115.9(3)

O(2)-C(6)-C(5) 115.9(3)

O(3)-C(7)-O(4) 122.9(4)

O(3)-C(7)-C(8) 117.6(4)

O(4)-C(7)-C(8) 119.5(4)

C(13)-C(8)-C(9) 115.2(4)

C(13)-C(8)-C(7) 123.5(4)

C(9)-C(8)-C(7) 121.3(4)

F(3)-C(9)-C(10) 117.0(4)

F(3)-C(9)-C(8) 120.8(4)

C(10)-C(9)-C(8) 122.2(4)

F(4)-C(10)-C(9) 119.3(4)

F(4)-C(10)-C(11) 119.2(4)

C(9)-C(10)-C(11) 121.6(4)

C(10)-C(11)-C(12) 117.4(4)

C(10)-C(11)-C(14) 120.7(4)

C(12)-C(11)-C(14) 122.0(4)

F(5)-C(12)-C(11) 119.8(4)

F(5)-C(12)-C(13) 119.5(4)

C(11)-C(12)-C(13) 120.7(4)

F(6)-C(13)-C(8) 120.6(4)

F(6)-C(13)-C(12) 116.4(4)

C(8)-C(13)-C(12) 123.0(4)

O(5)-C(14)-O(6) 123.0(4)

O(5)-C(14)-C(11) 118.9(4)

O(6)-C(14)-C(11) 118.0(4)

192

193

Table A6-3. Torsion angles [°] for Gd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)

________________________________________________________________________

O(2)#1-Gd(1)-O(1)-C(1) 20.9(4)

O(6)#2-Gd(1)-O(1)-C(1) -28.7(3)

O(7)-Gd(1)-O(1)-C(1) 165.8(3)

O(8)-Gd(1)-O(1)-C(1) 158.2(3)

O(4)-Gd(1)-O(1)-C(1) -117.6(3)

O(3)-Gd(1)-O(1)-C(1) -84.5(3)

O(5)#3-Gd(1)-O(1)-C(1) 93.7(3)

O(6)#3-Gd(1)-O(1)-C(1) 47.9(3)

O(2)#1-Gd(1)-O(3)-C(7) -175.6(3)

O(6)#2-Gd(1)-O(3)-C(7) -98.0(3)

O(1)-Gd(1)-O(3)-C(7) -43.0(3)

O(7)-Gd(1)-O(3)-C(7) 45.9(3)

O(8)-Gd(1)-O(3)-C(7) 108.5(3)

O(4)-Gd(1)-O(3)-C(7) 0.0(3)

O(5)#3-Gd(1)-O(3)-C(7) 140.4(3)

O(6)#3-Gd(1)-O(3)-C(7) -135.8(3)

O(2)#1-Gd(1)-O(4)-C(7) 5.5(4)

O(6)#2-Gd(1)-O(4)-C(7) 72.6(3)

O(1)-Gd(1)-O(4)-C(7) 145.4(3)

O(7)-Gd(1)-O(4)-C(7) -137.4(3)

O(8)-Gd(1)-O(4)-C(7) -65.3(3)

O(3)-Gd(1)-O(4)-C(7) 0.0(3)

O(5)#3-Gd(1)-O(4)-C(7) -139.3(3)

O(6)#3-Gd(1)-O(4)-C(7) 120.7(3)

Gd(1)-O(1)-C(1)-O(1)#6 -9.3(2)

Gd(1)-O(1)-C(1)-C(2) 170.7(2)

O(1)#6-C(1)-C(2)-C(3)#6 -131.2(3)

O(1)-C(1)-C(2)-C(3)#6 48.8(3)

O(1)#6-C(1)-C(2)-C(3) 48.8(3)

O(1)-C(1)-C(2)-C(3) -131.2(3)

C(3)#6-C(2)-C(3)-F(1) -177.5(5)

C(1)-C(2)-C(3)-F(1) 2.5(5)

C(3)#6-C(2)-C(3)-C(4) 0.4(3)

C(1)-C(2)-C(3)-C(4) -179.6(3)

194

F(1)-C(3)-C(4)-F(2) 0.7(6)

C(2)-C(3)-C(4)-F(2) -177.2(3)

F(1)-C(3)-C(4)-C(5) 177.1(3)

C(2)-C(3)-C(4)-C(5) -0.8(6)

F(2)-C(4)-C(5)-C(4)#6 176.7(5)

C(3)-C(4)-C(5)-C(4)#6 0.4(3)

F(2)-C(4)-C(5)-C(6) -3.3(5)

C(3)-C(4)-C(5)-C(6) -179.6(3)

Gd(1)#4-O(2)-C(6)-O(2)#6 9.0(2)

Gd(1)#4-O(2)-C(6)-C(5) -171.0(2)

C(4)-C(5)-C(6)-O(2)#6 -49.0(3)

C(4)#6-C(5)-C(6)-O(2)#6 131.0(3)

C(4)-C(5)-C(6)-O(2) 131.0(3)

C(4)#6-C(5)-C(6)-O(2) -49.0(3)

Gd(1)-O(3)-C(7)-O(4) -0.1(5)

Gd(1)-O(3)-C(7)-C(8) 179.2(4)

Gd(1)-O(4)-C(7)-O(3) 0.1(5)

Gd(1)-O(4)-C(7)-C(8) -179.2(4)

O(2)#1-Gd(1)-C(7)-O(3) 4.5(3)

O(6)#2-Gd(1)-C(7)-O(3) 75.8(3)

O(1)-Gd(1)-C(7)-O(3) 144.6(3)

O(7)-Gd(1)-C(7)-O(3) -138.9(3)

O(8)-Gd(1)-C(7)-O(3) -66.1(3)

O(4)-Gd(1)-C(7)-O(3) -179.9(5)

O(5)#3-Gd(1)-C(7)-O(3) -88.5(4)

O(6)#3-Gd(1)-C(7)-O(3) 76.4(4)

O(2)#1-Gd(1)-C(7)-O(4) -175.6(3)

O(6)#2-Gd(1)-C(7)-O(4) -104.3(3)

O(1)-Gd(1)-C(7)-O(4) -35.4(3)

O(7)-Gd(1)-C(7)-O(4) 41.0(3)

O(8)-Gd(1)-C(7)-O(4) 113.8(3)

________________________________________________________________________

195

Table A6-4. Hydrogen bonds for Gd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) [Å and °]

________________________________________________________________________


________________________________________________________________________

O(8)-H(8O)...O(9) 0.79(6) 1.93(6) 2.698(5) 165(6)

________________________________________________________________________

Figure A6-1: (a) shows a perspective drawing of the contents of the asymmetric unit for Gd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO). Nonhydrogen atoms are represented by thermal vibration ellipsoids drawn to encompass 50% of their electron density. Hydrogen atoms are represented by arbitrarily-small spheres, which are in no way representative of their true thermal motion.

196

Figure A6-2: show projections of the unit cell when viewed down the a-axis of the unit

cell in crystalline Gd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) with atoms represented as in Figure 1. Hydrogen atoms have been omitted for clarity.

197

APPENDIX A7: CRYSTAL STRUCTURE TABLES AND FIGURES FOR COMPOUND (7) [Eu2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)]


Table A8-1 Crystal data and structure refinement for Eu2(C8O4F4)3(EtOH)2(Et2NCHO)2 -

2(Et2NCHO) _______________________________________________________________________

Identification code a99o2_0m

Empirical formula C48 H56 Eu2 F12 N4 O18





2h (No. 15)


b = 11.229(1) Å, β = 108.658(1)°

c = 23.285(3) Å

Volume 5771.9(12) Å3

Z 4 formula units



F(000) 3000



Index ranges -32≤h≤31, -15≤k≤15, -32≤l≤32








Final R indices [7238 I>2σ(I) data] R1 = 0.0426, wR2 = 0.0899


Largest diff. peak and hole 1.909 and -2.036 e-/Å3 _______________________________________________________________________

198

Table A8-2. Bond lengths [Å] and angles [°] for Eu2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)

a,b,c

________________________________________________________________________

Eu(1)-O(2)#1 2.340(2)

Eu(1)-O(6)#2 2.386(3)

Eu(1)-O(1) 2.391(2)

Eu(1)-O(7) 2.407(3)

Eu(1)-O(8) 2.434(3)

Eu(1)-O(4) 2.479(3)

Eu(1)-O(3) 2.487(3)

Eu(1)-O(5)#3 2.511(3)

Eu(1)-O(6)#3 2.725(3)

F(1)-C(3) 1.345(4)

F(2)-C(4) 1.339(4)

F(3)-C(9) 1.343(4)

F(4)-C(10) 1.340(4)

F(5)-C(12) 1.340(4)

F(6)-C(13) 1.336(4)

O(1)-C(1) 1.249(3)

O(2)-C(6) 1.247(3)

O(3)-C(7) 1.248(4)

O(4)-C(7) 1.261(4)

O(5)-C(14) 1.234(4)

O(6)-C(14) 1.261(4)

C(1)-C(2) 1.505(7)

C(5)-C(6) 1.505(7)

C(7)-C(8) 1.502(5)

C(11)-C(14) 1.483(5)

C(2)-C(3) 1.383(4)

C(3)-C(4) 1.382(5)

C(4)-C(5) 1.381(4)

C(8)-C(13) 1.396(5)

C(8)-C(9) 1.382(5)

C(9)-C(10) 1.378(5)

C(10)-C(11) 1.396(5)

C(11)-C(12) 1.386(5)

C(12)-C(13) 1.387(5)

O(7)-C(15) 1.235(5)

O(9)-C(22) 1.224(6)

N(1)-C(15) 1.319(5)

N(2)-C(22) 1.340(6)

N(1)-C(16) 1.460(6)

N(1)-C(18) 1.472(6)

N(2)-C(23) 1.454(7)

N(2)-C(25) 1.457(6)

C(16)-C(17) 1.488(9)

C(18)-C(19) 1.520(9)

C(23)-C(24) 1.499(9)

C(25)-C(26) 1.484(7)

O(8)-C(20) 1.436(6) O(8)-H(8O) 0.81(6)

C(20)-C(21) 1.470(9)

O(2)#1-Eu(1)-O(6)#2 74.61(9)

O(2)#1-Eu(1)-O(1) 131.61(9)

O(6)#2-Eu(1)-O(1) 72.37(9)

O(2)#1-Eu(1)-O(7) 139.27(10)

O(6)#2-Eu(1)-O(7) 145.14(9)

O(1)-Eu(1)-O(7) 75.66(9)

O(2)#1-Eu(1)-O(8) 72.95(10)

O(6)#2-Eu(1)-O(8) 137.95(10)

O(1)-Eu(1)-O(8) 149.43(10)

O(7)-Eu(1)-O(8) 74.05(10)

O(2)#1-Eu(1)-O(4) 129.74(9)

O(6)#2-Eu(1)-O(4) 86.96(10)

O(1)-Eu(1)-O(4) 82.55(10)

O(7)-Eu(1)-O(4) 75.39(9)

O(8)-Eu(1)-O(4) 93.70(11)

O(2)#1-Eu(1)-O(3) 77.57(9)

O(6)#2-Eu(1)-O(3) 74.54(9)

199

O(1)-Eu(1)-O(3) 124.53(9)

O(7)-Eu(1)-O(3) 114.29(9)

O(8)-Eu(1)-O(3) 72.95(10)

O(4)-Eu(1)-O(3) 52.34(9)

O(2)#1-Eu(1)-O(5)#3 78.31(10)

O(6)#2-Eu(1)-O(5)#3 120.02(9)

O(1)-Eu(1)-O(5)#3 88.69(10)

O(7)-Eu(1)-O(5)#3 72.17(9)

O(8)-Eu(1)-O(5)#3 78.30(10)

O(4)-Eu(1)-O(5)#3 147.55(10)

O(3)-Eu(1)-O(5)#3 146.74(9)

O(2)#1-Eu(1)-O(6)#3 69.29(8)

O(6)#2-Eu(1)-O(6)#3 71.17(9)

O(1)-Eu(1)-O(6)#3 67.13(8)

O(7)-Eu(1)-O(6)#3 108.49(8)

O(8)-Eu(1)-O(6)#3 119.51(9)

O(4)-Eu(1)-O(6)#3 146.59(9)

O(3)-Eu(1)-O(6)#3 137.20(8)

O(5)#3-Eu(1)-O(6)#3 49.26(8)

C(1)-O(1)-Eu(1) 138.6(3)

C(6)-O(2)-Eu(1)#4 138.7(3)

C(7)-O(3)-Eu(1) 93.0(2)

C(7)-O(4)-Eu(1) 93.1(2)

C(14)-O(5)-Eu(1)#5 99.4(2)

C(14)-O(6)-Eu(1)#2 159.5(2)

C(14)-O(6)-Eu(1)#5 88.5(2)

Eu(1)#2-O(6)-Eu(1)#5 108.76(9)

O(1)#6-C(1)-O(1) 128.5(5)

O(1)#6-C(1)-C(2) 115.7(2)

O(1)-C(1)-C(2) 115.7(2)

C(3)-C(2)-C(3)#6 116.7(4)

C(3)-C(2)-C(1) 121.6(2)

C(3)#6-C(2)-C(1) 121.6(2)

F(1)-C(3)-C(4) 117.8(3)

F(1)-C(3)-C(2) 120.4(3)

C(4)-C(3)-C(2) 121.7(4)

F(2)-C(4)-C(5) 120.3(3)

F(2)-C(4)-C(3) 118.2(3)

C(5)-C(4)-C(3) 121.4(3)

C(4)#6-C(5)-C(4) 117.1(4)

C(4)#6-C(5)-C(6) 121.5(2)

C(4)-C(5)-C(6) 121.5(2)

O(2)#6-C(6)-O(2) 129.4(4)

O(2)#6-C(6)-C(5) 115.3(2)

O(2)-C(6)-C(5) 115.3(2)

O(3)-C(7)-O(4) 121.6(3)

O(3)-C(7)-C(8) 118.2(3)

O(4)-C(7)-C(8) 120.2(3)

C(9)-C(8)-C(13) 116.0(3)

C(9)-C(8)-C(7) 122.0(3)

C(13)-C(8)-C(7) 122.0(3)

F(3)-C(9)-C(10) 117.2(3)

F(3)-C(9)-C(8) 120.4(3)

C(10)-C(9)-C(8) 122.4(3)

F(4)-C(10)-C(9) 119.1(3)

F(4)-C(10)-C(11) 118.9(3)

C(9)-C(10)-C(11) 122.0(3)

C(12)-C(11)-C(10) 115.7(3)

C(12)-C(11)-C(14) 123.8(3)

C(10)-C(11)-C(14) 120.5(3)

F(5)-C(12)-C(11) 118.7(3)

F(5)-C(12)-C(13) 119.0(3)

C(11)-C(12)-C(13) 122.3(3)

F(6)-C(13)-C(12) 116.9(3)

F(6)-C(13)-C(8) 121.4(3)

C(12)-C(13)-C(8) 121.6(3)

O(5)-C(14)-O(6) 122.8(3)

O(5)-C(14)-C(11) 118.8(3)

O(6)-C(14)-C(11) 118.3(3)

200

Table A8-3. Torsion angles [°] for Eu2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)

________________________________________________________________________

O(2)#1-Eu(1)-O(1)-C(1) 20.4(3)

O(6)#2-Eu(1)-O(1)-C(1) -28.7(3)

O(7)-Eu(1)-O(1)-C(1) 165.4(3)

O(8)-Eu(1)-O(1)-C(1) 157.5(2)

O(4)-Eu(1)-O(1)-C(1) -117.9(3)

O(3)-Eu(1)-O(1)-C(1) -84.8(3)

O(5)#3-Eu(1)-O(1)-C(1) 93.4(3)

O(6)#3-Eu(1)-O(1)-C(1) 47.8(3)

O(2)#1-Eu(1)-O(3)-C(7) -175.4(2)

O(6)#2-Eu(1)-O(3)-C(7) -98.2(2)

O(1)-Eu(1)-O(3)-C(7) -43.1(3)

O(7)-Eu(1)-O(3)-C(7) 45.8(2)

O(8)-Eu(1)-O(3)-C(7) 108.8(2)

O(4)-Eu(1)-O(3)-C(7) 0.1(2)

O(5)#3-Eu(1)-O(3)-C(7) 140.2(2)

O(6)#3-Eu(1)-O(3)-C(7) -135.9(2)

O(2)#1-Eu(1)-O(4)-C(7) 5.6(3)

O(6)#2-Eu(1)-O(4)-C(7) 72.7(2)

O(1)-Eu(1)-O(4)-C(7) 145.3(2)

O(7)-Eu(1)-O(4)-C(7) -137.6(3)

O(8)-Eu(1)-O(4)-C(7) -65.2(2)

O(3)-Eu(1)-O(4)-C(7) -0.1(2)

O(5)#3-Eu(1)-O(4)-C(7) -139.1(2)

O(6)#3-Eu(1)-O(4)-C(7) 120.8(2)

Eu(1)-O(1)-C(1)-O(1)#6 -9.19(19)

Eu(1)-O(1)-C(1)-C(2) 170.82(19)

O(1)#6-C(1)-C(2)-C(3) 48.8(2)

O(1)-C(1)-C(2)-C(3) -131.2(2)

O(1)#6-C(1)-C(2)-C(3)#6 -131.2(2)

O(1)-C(1)-C(2)-C(3)#6 48.8(2)

C(3)#6-C(2)-C(3)-F(1) -176.8(4)

C(1)-C(2)-C(3)-F(1) 3.2(4)

C(3)#6-C(2)-C(3)-C(4) -0.1(2)

C(1)-C(2)-C(3)-C(4) 179.9(2)

201

F(1)-C(3)-C(4)-F(2) -0.4(5)

C(2)-C(3)-C(4)-F(2) -177.3(3)

F(1)-C(3)-C(4)-C(5) 177.0(3)

C(2)-C(3)-C(4)-C(5) 0.1(5)

F(2)-C(4)-C(5)-C(4)#6 177.3(4)

C(3)-C(4)-C(5)-C(4)#6 -0.1(2)

F(2)-C(4)-C(5)-C(6) -2.7(4)

C(3)-C(4)-C(5)-C(6) 179.9(2)

Eu(1)#4-O(2)-C(6)-O(2)#6 8.67(19)

Eu(1)#4-O(2)-C(6)-C(5) -171.32(19)

C(4)#6-C(5)-C(6)-O(2)#6 130.6(2)

C(4)-C(5)-C(6)-O(2)#6 -49.4(2)

C(4)#6-C(5)-C(6)-O(2) -49.4(2)

C(4)-C(5)-C(6)-O(2) 130.6(2)

Eu(1)-O(3)-C(7)-O(4) -0.1(4)

Eu(1)-O(3)-C(7)-C(8) 179.9(3)

Eu(1)-O(4)-C(7)-O(3) 0.1(4)

Eu(1)-O(4)-C(7)-C(8) -179.9(3)

O(3)-C(7)-C(8)-C(9) 28.8(5)

O(4)-C(7)-C(8)-C(9) -151.2(4)

O(3)-C(7)-C(8)-C(13) -149.9(4)

O(4)-C(7)-C(8)-C(13) 30.1(5)

C(13)-C(8)-C(9)-F(3) -179.4(4)

C(7)-C(8)-C(9)-F(3) 1.9(6)

C(13)-C(8)-C(9)-C(10) -0.3(6)

C(7)-C(8)-C(9)-C(10) -179.0(4)

F(3)-C(9)-C(10)-F(4) 0.3(6)

C(8)-C(9)-C(10)-F(4) -178.8(4)

F(3)-C(9)-C(10)-C(11) 179.2(4)

C(8)-C(9)-C(10)-C(11) 0.1(6)

F(4)-C(10)-C(11)-C(12) 179.7(3)

C(9)-C(10)-C(11)-C(12) 0.8(6)

F(4)-C(10)-C(11)-C(14) -0.7(6)

C(9)-C(10)-C(11)-C(14) -179.6(4)

C(10)-C(11)-C(12)-F(5) 179.7(3)

C(14)-C(11)-C(12)-F(5) 0.1(6)

202

C(10)-C(11)-C(12)-C(13) -1.6(6)

C(14)-C(11)-C(12)-C(13) 178.9(3)

F(5)-C(12)-C(13)-F(6) -2.4(5)

C(11)-C(12)-C(13)-F(6) 178.8(3)

F(5)-C(12)-C(13)-C(8) -179.8(3)

C(11)-C(12)-C(13)-C(8) 1.5(6)

C(9)-C(8)-C(13)-F(6) -177.7(3)

C(7)-C(8)-C(13)-F(6) 1.0(6)

C(9)-C(8)-C(13)-C(12) -0.5(6)

C(7)-C(8)-C(13)-C(12) 178.3(3)

Eu(1)#5-O(5)-C(14)-O(6) -1.4(4)

Eu(1)#5-O(5)-C(14)-C(11) -179.7(3)

Eu(1)#2-O(6)-C(14)-O(5) 149.5(5)

Eu(1)#5-O(6)-C(14)-O(5) 1.3(4)

Eu(1)#2-O(6)-C(14)-C(11) -32.3(8)

Eu(1)#5-O(6)-C(14)-C(11) 179.5(3)

C(12)-C(11)-C(14)-O(5) -97.1(4)

C(10)-C(11)-C(14)-O(5) 83.4(5)

C(12)-C(11)-C(14)-O(6) 84.6(4)

C(10)-C(11)-C(14)-O(6) -95.0(4)

O(2)#1-Eu(1)-O(7)-C(15) 97.9(4)

O(6)#2-Eu(1)-O(7)-C(15) -64.9(4)

O(1)-Eu(1)-O(7)-C(15) -41.0(3)

O(8)-Eu(1)-O(7)-C(15) 134.8(4)

O(4)-Eu(1)-O(7)-C(15) -126.9(4)

O(3)-Eu(1)-O(7)-C(15) -162.8(3)

O(5)#3-Eu(1)-O(7)-C(15) 52.3(3)

O(6)#3-Eu(1)-O(7)-C(15) 18.4(4)

Eu(1)-O(7)-C(15)-N(1) -175.4(3)

C(16)-N(1)-C(15)-O(7) 2.7(7)

C(18)-N(1)-C(15)-O(7) -178.9(5)

C(15)-N(1)-C(16)-C(17) 89.2(6)

C(18)-N(1)-C(16)-C(17) -89.2(6)

C(15)-N(1)-C(18)-C(19) 105.0(6)

C(16)-N(1)-C(18)-C(19) -76.6(7) ________________________________________________________________________

203

Table A8-4. Hydrogen bonds for Eu2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) [Å and °]a,b

________________________________________________________________________


________________________________________________________________________

O(8)-H(8O)...O(9) 0.81(6) 1.92(6) 2.696(4) 160(5)

________________________________________________________________________

Figure A8-1: shows a perspective drawing of the contents of the asymmetric unit

for Eu2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO). The europium atom is represented by a large cross-hatched sphere; fluorine atoms are represented by medium-sized dotted spheres; oxygen and nitrogen atoms are represented by medium-sized shaded spheres and carbon and hydrogen atoms are represented by medium and small open spheres, respectively.

204

Figure A8-2: show projections of the unit cell when viewed down the b-axis of the unit cell in crystalline Eu2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) with atoms represented as in Figure A8-1. Hydrogen atoms have been omitted for clarity.

205

APPENDIX A8: CRYSTAL STRUCTURE TABLES AND FIGURES FOR COMPOUND (8) [La2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)]


Table A6-1 Crystal data and structure refinement for La2(C8O4F4)3(EtOH)2(Et2NCHO)2 -

2(Et2NCHO) _______________________________________________________________________


Empirical formula C48 H56 F12 La2 N4 O18




Crystal system Monoclinic Space group C2/c– C 6

2h (No. 15)


b = 11.3837(8) Å, β = 108.640(1)°

c = 23.623(2) Å

Volume 5998.9(7) Å3

Z 4



F(000) 2952



Index ranges -33≤h≤33, -16≤k≤15, -33≤l≤33










________________________________________________________________________

206

Table A7-2. Bond lengths [Å] and angles [°] for La2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)

________________________________________________________________________

La(1)-O(2)#1 2.439(2)

La(1)-O(1) 2.482(2)

La(1)-O(6)#2 2.494(2)

La(1)-O(7) 2.508(2)

La(1)-O(8) 2.527(2)

La(1)-O(3) 2.570(2)

La(1)-O(4) 2.581(2)

La(1)-O(5)#3 2.625(2)

La(1)-O(6)#3 2.761(2)

F(1)-C(3) 1.344(3)

F(2)-C(4) 1.340(3)

F(3)-C(9) 1.336(4)

F(4)-C(10) 1.339(4)

F(5)-C(12) 1.341(3)

F(6)-C(13) 1.337(4)

O(1)-C(1) 1.248(3)

O(2)-C(6) 1.240(3)

O(3)-C(7) 1.247(4)

O(4)-C(7) 1.251(4)

O(5)-C(14) 1.234(4)

O(6)-C(14) 1.257(4)

C(1)-C(2) 1.509(5)

C(5)-C(6) 1.512(5)

C(7)-C(8) 1.514(4)

C(11)-C(14) 1.505(4)

C(2)-C(3) 1.380(4)

C(3)-C(4) 1.381(4)

C(4)-C(5) 1.379(4)

C(8)-C(13) 1.390(4)

C(8)-C(9) 1.393(4)

C(9)-C(10) 1.372(4)

C(10)-C(11) 1.380(4)

C(11)-C(12) 1.382(4)

C(12)-C(13) 1.382(4)

O(7)-C(15) 1.233(4)

O(9)-C(22) 1.228(5)

N(1)-C(15) 1.320(4)

N(2)-C(22) 1.331(5)

N(1)-C(16) 1.464(6)

N(1)-C(18) 1.470(5)

N(2)-C(23) 1.456(7)

N(2)-C(25) 1.462(5)

C(16)-C(17) 1.486(7)

C(18)-C(19) 1.520(8)

C(23)-C(24) 1.495(8)

C(25)-C(26) 1.491(6)

O(8)-C(20) 1.416(7) O(8)-H(8O) 0.81(5)

C(20)-C(21) 1.354(9)

O(2)#1-La(1)-O(1) 130.63(7)

O(2)#1-La(1)-O(6)#2 73.07(7)

O(1)-La(1)-O(6)#2 71.49(7)

O(2)#1-La(1)-O(7) 140.06(8)

O(1)-La(1)-O(7) 75.84(7)

O(6)#2-La(1)-O(7) 145.30(7)

O(2)#1-La(1)-O(8) 72.76(8)

O(1)-La(1)-O(8) 151.06(8)

O(6)#2-La(1)-O(8) 137.34(8)

O(7)-La(1)-O(8) 75.46(9)

O(2)#1-La(1)-O(3) 78.19(8)

O(1)-La(1)-O(3) 122.88(8)

O(6)#2-La(1)-O(3) 75.05(7)

O(7)-La(1)-O(3) 115.01(8)

O(8)-La(1)-O(3) 73.61(8)

O(2)#1-La(1)-O(4) 128.61(8)

O(1)-La(1)-O(4) 83.70(8)

207

O(6)#2-La(1)-O(4) 88.84(8)

O(7)-La(1)-O(4) 76.16(8)

O(8)-La(1)-O(4) 92.98(9)

O(3)-La(1)-O(4) 50.52(7)

O(2)#1-La(1)-O(5)#3 78.92(8)

O(1)-La(1)-O(5)#3 89.06(8)

O(6)#2-La(1)-O(5)#3 118.62(7)

O(7)-La(1)-O(5)#3 71.49(8)

O(8)-La(1)-O(5)#3 78.44(8)

O(3)-La(1)-O(5)#3 148.00(8)

O(4)-La(1)-O(5)#3 147.64(8)

O(2)#1-La(1)-O(6)#3 69.42(7)

O(1)-La(1)-O(6)#3 67.23(7)

O(6)#2-La(1)-O(6)#3 71.00(7)

O(7)-La(1)-O(6)#3 106.66(7)

O(8)-La(1)-O(6)#3 118.35(8)

O(3)-La(1)-O(6)#3 138.33(7)

O(4)-La(1)-O(6)#3 148.46(8)

O(5)#3-La(1)-O(6)#3 48.06(7)

C(1)-O(1)-La(1) 139.2(2)

C(6)-O(2)-La(1)#4 140.1(2)

C(7)-O(3)-La(1) 93.41(18)

C(7)-O(4)-La(1) 92.76(19)

C(14)-O(5)-La(1)#5 97.56(19)

C(14)-O(6)-La(1)#2 157.7(2)

C(14)-O(6)-La(1)#5 90.54(18)

La(1)#2-O(6)-La(1)#5 108.94(7)

O(1)-C(1)-O(1)#6 128.8(4)

O(1)-C(1)-C(2) 115.58(18)

O(1)#6-C(1)-C(2) 115.58(18)

C(3)-C(2)-C(3)#6 116.9(4)

C(3)-C(2)-C(1) 121.57(18)

C(3)#6-C(2)-C(1) 121.57(18)

F(1)-C(3)-C(2) 120.4(3)

F(1)-C(3)-C(4) 117.8(3)

C(2)-C(3)-C(4) 121.7(3)

F(2)-C(4)-C(5) 120.4(3)

F(2)-C(4)-C(3) 118.5(3)

C(5)-C(4)-C(3) 121.0(3)

C(4)#6-C(5)-C(4) 117.6(4)

C(4)-C(5)-C(6) 121.19(18)

O(2)#6-C(6)-O(2) 128.9(4)

O(2)-C(6)-C(5) 115.57(18)

O(3)-C(7)-O(4) 123.3(3)

O(3)-C(7)-C(8) 117.7(3)

O(4)-C(7)-C(8) 119.0(3)

C(13)-C(8)-C(9) 116.0(3)

C(13)-C(8)-C(7) 122.6(3)

C(9)-C(8)-C(7) 121.4(3)

F(3)-C(9)-C(10) 117.6(3)

F(3)-C(9)-C(8) 120.6(3)

C(10)-C(9)-C(8) 121.8(3)

F(4)-C(10)-C(9) 119.1(3)

F(4)-C(10)-C(11) 118.8(3)

C(9)-C(10)-C(11) 122.0(3)

C(10)-C(11)-C(12) 116.7(3)

C(10)-C(11)-C(14) 120.7(3)

C(12)-C(11)-C(14) 122.6(3)

F(5)-C(12)-C(13) 118.9(3)

F(5)-C(12)-C(11) 119.4(3)

C(13)-C(12)-C(11) 121.7(3)

F(6)-C(13)-C(12) 117.5(3)

F(6)-C(13)-C(8) 120.7(3)

C(12)-C(13)-C(8) 121.7(3)

O(5)-C(14)-O(6) 123.8(3)

O(5)-C(14)-C(11) 118.6(3)

O(6)-C(14)-C(11) 117.6(3)

C(15)-O(7)-La(1) 129.0(2)

C(20)-O(8)-La(1) 127.2(4)

C(20)-O(8)-H(8O) 103(3)

La(1)-O(8)-H(8O) 122(3)

208

Table A7-3. Torsion angles [°] for La2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO).

________________________________________________________________________

O(2)#1-La(1)-O(1)-C(1) 16.3(3)

O(6)#2-La(1)-O(1)-C(1) -29.9(2)

O(7)-La(1)-O(1)-C(1) 161.9(3)

O(8)-La(1)-O(1)-C(1) 154.5(2)

O(3)-La(1)-O(1)-C(1) -87.2(2)

O(4)-La(1)-O(1)-C(1) -120.8(2)

O(5)#3-La(1)-O(1)-C(1) 90.8(2)

O(6)#3-La(1)-O(1)-C(1) 46.7(2)

O(2)#1-La(1)-O(3)-C(7) -176.7(2)

O(1)-La(1)-O(3)-C(7) -45.7(2)

O(6)#2-La(1)-O(3)-C(7) -101.3(2)

O(7)-La(1)-O(3)-C(7) 43.2(2)

O(8)-La(1)-O(3)-C(7) 108.0(2)

O(4)-La(1)-O(3)-C(7) -0.22(19)

O(5)#3-La(1)-O(3)-C(7) 138.1(2)

O(6)#3-La(1)-O(3)-C(7) -137.56(18)

O(2)#1-La(1)-O(4)-C(7) 4.6(3)

O(1)-La(1)-O(4)-C(7) 143.2(2)

O(6)#2-La(1)-O(4)-C(7) 71.7(2)

O(7)-La(1)-O(4)-C(7) -139.9(2)

O(8)-La(1)-O(4)-C(7) -65.6(2)

O(3)-La(1)-O(4)-C(7) 0.22(19)

O(5)#3-La(1)-O(4)-C(7) -138.6(2)

O(6)#3-La(1)-O(4)-C(7) 120.8(2)

La(1)-O(1)-C(1)-O(1)#6 -7.82(16)

La(1)-O(1)-C(1)-C(2) 172.17(16)

O(1)-C(1)-C(2)-C(3) -130.22(19)

O(1)#6-C(1)-C(2)-C(3) 49.78(19)

O(1)-C(1)-C(2)-C(3)#6 49.78(19)

O(1)#6-C(1)-C(2)-C(3)#6 -130.22(19)

C(3)#6-C(2)-C(3)-F(1) -176.5(3)

C(1)-C(2)-C(3)-F(1) 3.5(3)

C(3)#6-C(2)-C(3)-C(4) -0.2(2)

C(1)-C(2)-C(3)-C(4) 179.8(2)

209

F(1)-C(3)-C(4)-F(2) -0.7(4)

C(2)-C(3)-C(4)-F(2) -177.1(2)

F(1)-C(3)-C(4)-C(5) 176.8(2)

C(2)-C(3)-C(4)-C(5) 0.4(4)

F(2)-C(4)-C(5)-C(4)#6 177.3(3)

C(3)-C(4)-C(5)-C(4)#6 -0.2(2)

F(2)-C(4)-C(5)-C(6) -2.7(3)

C(3)-C(4)-C(5)-C(6) 179.8(2)

La(1)#4-O(2)-C(6)-O(2)#6 6.00(17)

La(1)#4-O(2)-C(6)-C(5) -174.00(17)

C(4)#6-C(5)-C(6)-O(2)#6 128.48(19)

C(4)-C(5)-C(6)-O(2)#6 -51.52(19)

C(4)#6-C(5)-C(6)-O(2) -51.52(19)

C(4)-C(5)-C(6)-O(2) 128.48(19)

La(1)-O(3)-C(7)-O(4) 0.4(4)

La(1)-O(3)-C(7)-C(8) -179.8(2)

La(1)-O(4)-C(7)-O(3) -0.4(4)

La(1)-O(4)-C(7)-C(8) 179.8(3)

O(3)-C(7)-C(8)-C(13) -147.3(3)

O(4)-C(7)-C(8)-C(13) 32.5(5)

O(3)-C(7)-C(8)-C(9) 31.6(5)

O(4)-C(7)-C(8)-C(9) -148.7(3)

C(13)-C(8)-C(9)-F(3) -179.2(3)

C(7)-C(8)-C(9)-F(3) 1.9(5)

C(13)-C(8)-C(9)-C(10) -1.1(5)

C(7)-C(8)-C(9)-C(10) 180.0(3)

F(3)-C(9)-C(10)-F(4) -0.3(5)

C(8)-C(9)-C(10)-F(4) -178.4(3)

F(3)-C(9)-C(10)-C(11) 179.3(3)

C(8)-C(9)-C(10)-C(11) 1.1(6)

F(4)-C(10)-C(11)-C(12) 179.3(3)

C(9)-C(10)-C(11)-C(12) -0.2(5)

F(4)-C(10)-C(11)-C(14) 0.3(5)

C(9)-C(10)-C(11)-C(14) -179.3(3)

C(10)-C(11)-C(12)-F(5) 179.8(3)

________________________________________________________________________

210

Table A7-4. Hydrogen bonds for La2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) [Å

and °].

________________________________________________________________________


________________________________________________________________________

O(8)-H(8O)...O(9) 0.81(5) 1.89(5) 2.691(4) 166(5)

________________________________________________________________________

Figure A7-1: A perspective drawing of the contents of the asymmetric unit for

La2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO). Nonhydrogen atoms are represented by thermal vibration ellipsoids drawn to encompass 50% of their electron density. Hydrogen atoms are represented by arbitrarily-small spheres, which are in no way representative of their true thermal motion.

211

Figure A7-2: A projection of the unit cell when viewed down the b-axis in crystalline La2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) with atoms represented as arbitrarily small spheres, which are in no way representative of their true thermal motion.. Hydrogen atoms have been omitted for clarity.

212

APPENDIX A9: CRYSTAL STRUCTURE TABLES AND FIGURES FOR COMPOUND (9) [Nd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)]


Table A9-1 Crystal data and structure refinement for Nd2(C8O4F4)3(EtOH)2(Et2NCHO)2 -

2(Et2NCHO) ________________________________________________________________________


Empirical formula C48 H56 F12 N4 Nd2 O18




Crystal system Monoclinic Space group C2/c– C 6

2h (No. 15)


b = 11.301(1) Å, β = 108.634(1)°

c = 23.425(2) Å

Volume 5869.4(9) Å3

Z 4



F(000) 2976



Index ranges -30≤h≤30, -14≤k≤14, -30≤l≤29











________________________________________________________________________

213

Table 3. Bond lengths [Å] and angles [°] for Nd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)

________________________________________________________________________

Nd(1)-O(2)#1 2.381(3)

Nd(1)-O(1) 2.431(3)

Nd(1)-O(6)#2 2.436(3)

Nd(1)-O(7) 2.447(3)

Nd(1)-O(8) 2.475(4)

Nd(1)-O(3) 2.523(3)

Nd(1)-O(4) 2.527(3)

Nd(1)-O(5)#3 2.559(3)

Nd(1)-O(6)#3 2.729(3)

F(1)-C(3) 1.349(5)

F(2)-C(4) 1.337(5)

F(3)-C(9) 1.336(5)

F(4)-C(10) 1.334(5)

F(5)-C(12) 1.345(5)

F(6)-C(13) 1.336(5)

O(1)-C(1) 1.244(4)

O(2)-C(6) 1.247(4)

O(3)-C(7) 1.243(5)

O(4)-C(7) 1.260(6)

O(5)-C(14) 1.234(6)

O(6)-C(14) 1.253(5)

C(1)-C(2) 1.518(8)

C(5)-C(6) 1.505(9)

C(7)-C(8) 1.513(6)

C(11)-C(14) 1.500(6)

C(2)-C(3) 1.382(6)

C(3)-C(4) 1.373(6)

C(4)-C(5) 1.387(6)

C(8)-C(13) 1.387(6)

C(8)-C(9) 1.389(6)

C(9)-C(10) 1.373(7)

C(10)-C(11) 1.396(6)

C(11)-C(12) 1.375(6)

C(12)-C(13) 1.389(6)

O(7)-C(15) 1.232(6)

O(9)-C(22) 1.228(7)

N(1)-C(15) 1.316(7)

N(2)-C(22) 1.344(7)

N(1)-C(16) 1.459(8)

N(1)-C(18) 1.473(8)

N(2)-C(23) 1.455(9)

N(2)-C(25) 1.454(7)

C(16)-C(17) 1.485(10)

C(18)-C(19) 1.504(11)

C(23)-C(24) 1.506(11)

C(25)-C(26) 1.490(9)

O(8)-C(20) 1.433(8) O(8)-H(8O) 0.77(5)

C(20)-C(21) 1.454(12)

O(2)#1-Nd(1)-O(1) 131.51(11)

O(2)#1-Nd(1)-O(6)#2 74.03(11)

O(1)-Nd(1)-O(6)#2 71.98(11)

O(2)#1-Nd(1)-O(7) 139.54(12)

O(1)-Nd(1)-O(7) 75.81(11)

O(6)#2-Nd(1)-O(7) 145.29(11)

O(2)#1-Nd(1)-O(8) 72.80(12)

O(1)-Nd(1)-O(8) 150.03(12)

O(6)#2-Nd(1)-O(8) 137.80(12)

O(7)-Nd(1)-O(8) 74.46(13)

O(2)#1-Nd(1)-O(3) 77.67(11)

O(1)-Nd(1)-O(3) 123.58(12)

O(6)#2-Nd(1)-O(3) 74.65(11)

O(7)-Nd(1)-O(3) 114.55(11)

O(8)-Nd(1)-O(3) 73.40(12)

O(2)#1-Nd(1)-O(4) 129.13(11)

O(1)-Nd(1)-O(4) 82.93(12)

214

O(6)#2-Nd(1)-O(4) 87.91(12)

O(7)-Nd(1)-O(4) 75.53(12)

O(8)-Nd(1)-O(4) 93.25(13)

O(3)-Nd(1)-O(4) 51.57(11)

O(2)#1-Nd(1)-O(5)#3 78.67(12)

O(1)-Nd(1)-O(5)#3 89.02(12)

O(6)#2-Nd(1)-O(5)#3 119.40(11)

O(7)-Nd(1)-O(5)#3 71.97(12)

O(8)-Nd(1)-O(5)#3 78.32(12)

O(3)-Nd(1)-O(5)#3 147.35(12)

O(4)-Nd(1)-O(5)#3 147.50(12)

O(2)#1-Nd(1)-O(6)#3 69.64(10)

O(1)-Nd(1)-O(6)#3 67.24(10)

O(6)#2-Nd(1)-O(6)#3 71.08(11)

O(7)-Nd(1)-O(6)#3 107.77(10)

O(8)-Nd(1)-O(6)#3 119.10(11)

O(3)-Nd(1)-O(6)#3 137.67(10)

O(4)-Nd(1)-O(6)#3 147.42(11)

O(5)#3-Nd(1)-O(6)#3 48.76(10)

C(1)-O(1)-Nd(1) 138.4(3)

C(6)-O(2)-Nd(1)#4 138.9(3)

C(7)-O(3)-Nd(1) 93.1(3)

C(7)-O(4)-Nd(1) 92.5(3)

C(14)-O(5)-Nd(1)#5 98.3(3)

C(14)-O(6)-Nd(1)#2 158.3(3)

C(14)-O(6)-Nd(1)#5 89.7(3)

Nd(1)#2-O(6)-Nd(1)#5 108.85(11)

O(1)#6-C(1)-O(1) 129.5(6)

O(1)#6-C(1)-C(2) 115.2(3)

O(1)-C(1)-C(2) 115.2(3)

C(3)-C(2)-C(3)#6 116.3(6)

C(3)-C(2)-C(1) 121.9(3)

C(3)#6-C(2)-C(1) 121.9(3)

F(1)-C(3)-C(4) 117.9(4)

F(1)-C(3)-C(2) 119.8(4)

C(4)-C(3)-C(2) 122.2(5)

F(2)-C(4)-C(3) 118.8(4)

F(2)-C(4)-C(5) 120.0(4)

C(3)-C(4)-C(5) 121.2(5)

C(4)-C(5)-C(4)#6 116.9(6)

C(4)-C(5)-C(6) 121.6(3)

C(4)#6-C(5)-C(6) 121.6(3)

O(2)-C(6)-O(2)#6 129.7(6)

O(2)-C(6)-C(5) 115.2(3)

O(2)#6-C(6)-C(5) 115.2(3)

O(3)-C(7)-O(4) 122.7(4)

O(3)-C(7)-C(8) 118.0(4)

O(4)-C(7)-C(8) 119.2(4)

C(13)-C(8)-C(9) 116.4(4)

C(13)-C(8)-C(7) 122.4(4)

C(9)-C(8)-C(7) 121.3(4)

F(3)-C(9)-C(10) 117.3(4)

F(3)-C(9)-C(8) 120.7(4)

C(10)-C(9)-C(8) 122.0(4)

F(4)-C(10)-C(9) 119.6(4)

F(4)-C(10)-C(11) 118.7(4)

C(9)-C(10)-C(11) 121.7(4)

C(12)-C(11)-C(10) 116.3(4)

C(12)-C(11)-C(14) 123.4(4)

C(10)-C(11)-C(14) 120.3(4)

F(5)-C(12)-C(11) 119.2(4)

F(5)-C(12)-C(13) 118.7(4)

C(11)-C(12)-C(13) 122.1(4)

F(6)-C(13)-C(8) 121.2(4)

F(6)-C(13)-C(12) 117.4(4)

C(8)-C(13)-C(12) 121.4(4)

O(5)-C(14)-O(6) 123.2(4)

O(5)-C(14)-C(11) 118.4(4)

O(6)-C(14)-C(11) 118.3(4)

215

216

216

Table 6. Torsion angles [°] for Nd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO)

________________________________________________________________________

O(2)#1-Nd(1)-O(1)-C(1) 18.3(4)

O(6)#2-Nd(1)-O(1)-C(1) -29.3(3)

O(7)-Nd(1)-O(1)-C(1) 163.8(4)

O(8)-Nd(1)-O(1)-C(1) 156.4(3)

O(3)-Nd(1)-O(1)-C(1) -85.9(4)

O(4)-Nd(1)-O(1)-C(1) -119.4(4)

O(5)#3-Nd(1)-O(1)-C(1) 92.2(4)

O(6)#3-Nd(1)-O(1)-C(1) 47.3(3)

C(7)-Nd(1)-O(1)-C(1) -104.0(4)

C(14)#3-Nd(1)-O(1)-C(1) 70.8(4)

O(2)#1-Nd(1)-O(3)-C(7) -176.4(3)

O(1)-Nd(1)-O(3)-C(7) -44.4(3)

O(6)#2-Nd(1)-O(3)-C(7) -99.8(3)

O(7)-Nd(1)-O(3)-C(7) 44.5(3)

O(8)-Nd(1)-O(3)-C(7) 108.1(3)

O(4)-Nd(1)-O(3)-C(7) 0.0(3)

O(5)#3-Nd(1)-O(3)-C(7) 139.2(3)

O(6)#3-Nd(1)-O(3)-C(7) -136.6(3)

C(14)#3-Nd(1)-O(3)-C(7) -173.8(3)

O(2)#1-Nd(1)-O(4)-C(7) 4.6(4)

O(1)-Nd(1)-O(4)-C(7) 144.1(3)

O(6)#2-Nd(1)-O(4)-C(7) 72.0(3)

O(7)-Nd(1)-O(4)-C(7) -138.8(3)

O(8)-Nd(1)-O(4)-C(7) -65.7(3)

O(3)-Nd(1)-O(4)-C(7) 0.0(3)

O(5)#3-Nd(1)-O(4)-C(7) -139.0(3)

O(6)#3-Nd(1)-O(4)-C(7) 120.8(3)

C(14)#3-Nd(1)-O(4)-C(7) 171.7(3)

Nd(1)-O(1)-C(1)-O(1)#6 -8.5(2)

Nd(1)-O(1)-C(1)-C(2) 171.5(2)

O(1)#6-C(1)-C(2)-C(3) 49.4(3)

O(1)-C(1)-C(2)-C(3) -130.6(3)

O(1)#6-C(1)-C(2)-C(3)#6 -130.6(3)

O(1)-C(1)-C(2)-C(3)#6 49.4(3)

217

217

C(3)#6-C(2)-C(3)-F(1) -177.3(5)

C(1)-C(2)-C(3)-F(1) 2.7(5)

C(3)#6-C(2)-C(3)-C(4) 0.1(3)

C(1)-C(2)-C(3)-C(4) -179.9(3)

F(1)-C(3)-C(4)-F(2) -0.1(6)

C(2)-C(3)-C(4)-F(2) -177.5(4)

F(1)-C(3)-C(4)-C(5) 177.2(3)

C(2)-C(3)-C(4)-C(5) -0.2(7)

F(2)-C(4)-C(5)-C(4)#6 177.4(5)

C(3)-C(4)-C(5)-C(4)#6 0.1(3)

F(2)-C(4)-C(5)-C(6) -2.6(5)

C(3)-C(4)-C(5)-C(6) -179.9(3)

Nd(1)#4-O(2)-C(6)-O(2)#6 7.1(2)

Nd(1)#4-O(2)-C(6)-C(5) -172.9(2)

C(4)-C(5)-C(6)-O(2) 129.5(3)

C(4)#6-C(5)-C(6)-O(2) -50.5(3)

C(4)-C(5)-C(6)-O(2)#6 -50.5(3)

C(4)#6-C(5)-C(6)-O(2)#6 129.5(3)

Nd(1)-O(3)-C(7)-O(4) 0.1(5)

Nd(1)-O(3)-C(7)-C(8) -179.9(4)

Nd(1)-O(4)-C(7)-O(3) -0.1(5)

Nd(1)-O(4)-C(7)-C(8) 179.9(4)

O(3)-C(7)-C(8)-C(13) -148.5(5)

O(4)-C(7)-C(8)-C(13) 31.5(7)

Nd(1)-C(7)-C(8)-C(13) -155(25)

O(3)-C(7)-C(8)-C(9) 30.6(7)

O(4)-C(7)-C(8)-C(9) -149.4(5)

Nd(1)-C(7)-C(8)-C(9) 24(26)

C(13)-C(8)-C(9)-F(3) -179.5(5)

C(7)-C(8)-C(9)-F(3) 1.3(7)

C(13)-C(8)-C(9)-C(10) -0.2(8)

C(7)-C(8)-C(9)-C(10) -179.4(5)

F(3)-C(9)-C(10)-F(4) -0.1(8)

C(8)-C(9)-C(10)-F(4) -179.3(5)

F(3)-C(9)-C(10)-C(11) 179.7(5)

C(8)-C(9)-C(10)-C(11) 0.4(8)

218

218

F(4)-C(10)-C(11)-C(12) -179.9(4)

C(9)-C(10)-C(11)-C(12) 0.3(7)

F(4)-C(10)-C(11)-C(14) 0.2(7)

C(9)-C(10)-C(11)-C(14) -179.5(5)

C(10)-C(11)-C(12)-F(5) -179.9(4)

C(14)-C(11)-C(12)-F(5) -0.1(7)

C(10)-C(11)-C(12)-C(13) -1.2(7)

C(14)-C(11)-C(12)-C(13) 178.7(4)

C(9)-C(8)-C(13)-F(6) -178.1(4)

C(7)-C(8)-C(13)-F(6) 1.0(7)

C(9)-C(8)-C(13)-C(12) -0.6(7)

C(7)-C(8)-C(13)-C(12) 178.5(4)

F(5)-C(12)-C(13)-F(6) -2.3(7)

C(11)-C(12)-C(13)-F(6) 179.0(4)

F(5)-C(12)-C(13)-C(8) -179.9(4)

C(11)-C(12)-C(13)-C(8) 1.4(7)

Nd(1)#5-O(5)-C(14)-O(6) -1.4(5)

Nd(1)#5-O(5)-C(14)-C(11) -179.7(3)

Nd(1)#2-O(6)-C(14)-O(5) 150.6(6)

Nd(1)#5-O(6)-C(14)-O(5) 1.3(5)

Nd(1)#2-O(6)-C(14)-C(11) -31.2(10)

Nd(1)#5-O(6)-C(14)-C(11) 179.6(3)

Nd(1)#2-O(6)-C(14)-Nd(1)#5 149.3(8)

C(12)-C(11)-C(14)-O(5) -97.0(6)

C(10)-C(11)-C(14)-O(5) 82.9(6)

C(12)-C(11)-C(14)-O(6) 84.7(6)

C(10)-C(11)-C(14)-O(6) -95.4(5)

C(12)-C(11)-C(14)-Nd(1)#5 -101(4)

C(10)-C(11)-C(14)-Nd(1)#5 79(4)

O(2)#1-Nd(1)-O(7)-C(15) 99.0(5)

O(1)-Nd(1)-O(7)-C(15) -40.2(4)

O(6)#2-Nd(1)-O(7)-C(15) -62.4(5)

O(8)-Nd(1)-O(7)-C(15) 136.0(5)

O(3)-Nd(1)-O(7)-C(15) -160.9(4)

O(4)-Nd(1)-O(7)-C(15) -126.4(5)

________________________________________________________________________

219

219

Table 7. Hydrogen bonds for Nd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) [Å and °].

________________________________________________________________________


________________________________________________________________________

O(8)-H(8O)...O(9) 0.77(5) 1.96(5) 2.696(6) 162(5)

________________________________________________________________________

Figure A9-1: A perspective drawing of the contents of the asymmetric unit for Nd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO). The neodymium atom is represented by a large cross-hatched sphere; fluorine atoms are represented by medium-sized dotted spheres; oxygen and nitrogen atoms are represented by medium-sized shaded spheres and carbon and hydrogen atoms are represented by medium and small open spheres, respectively.

220

220

Figure A9-2: A perspective drawing of the coordination sphere about a single Nd atom in crystalline Nd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) with atoms represented as in Figure A9-1.

Figure A9-3: A projection of the unit cell when viewed down the b-axis in crystalline Nd2(C8O4F4)3(EtOH)2(Et2NCHO)2 - 2(Et2NCHO) with atoms represented as in Figure A9-1. Hydrogen atoms have been omitted for clarity.

221

0

20

40

60

80

100

120

0 100 200 300 400 500 600 700 800 900 1000Temperature (oC)

We

igh

t %

ST

R

0

20

40

60

80

100

120

0 100 200 300 400 500 600 700 800 900 1000

Temperature (oC)

Wei

gh

t %

ST

R

APPENDIX B: CHARACTERIZATION OF FRAMEWORKS 1-9

Figure B1: TGA of compound 1 using solvothermal (ST) and reflux (R) methods from

40oC-900oC at 5oC/min under air (40mL/min).



222

40

50

60

70

80

90

100

110

0 100 200 300 400 500 600 700 800 900 1000

temperature (oC)

We

igh

t %

ST

R



Figure B4: X-ray powder diffraction spectra comparing the solvothermal method with

the reflux method for compound 1.

0 1 0 2 0 3 0 4 0 5 0 6 0

0

1 0 0

2 0 0

3 0 0

4 0 0

5 0 0

6 0 0

7 0 0

8 0 0

re f lu x

s e a le d tu b e

Inte

nsity

2 - S c a le

L a2(2 ,5 -T D C )

3(D M F )

2(H

2O )-D M F (1 )

223

Figure B5: X-ray powder diffraction spectra comparing the solvothermal method with the

reflux method for compound 2.

Figure B6: X-ray powder diffraction spectra comparing the solvothermal method with the

reflux method for compound 3.

0 1 0 2 0 3 0 4 0 5 0 6 0

0

5 0

1 0 0

1 5 0

2 0 0

2 5 0

3 0 0

3 5 0

4 0 0

4 5 0

5 0 0

re f lu x

s e a le d tu b e

Inte

nsi

ty

2 - S c a le

G d2(2 ,5 -T D C )

3(D M F )

2(H

2O ) (2 )

0 1 0 2 0 3 0 4 0 5 0 6 0-2 0

0

2 0

4 0

6 0

8 0

1 0 0

1 2 0

1 4 0

1 6 0

1 8 0

re f lu x

s e a le d tu b e

Inte

nsi

ty

2 - S c a le

E u2(2 ,5 -T D C )

3(D M F )

2(H

2O ) (3 )

224

0

50

100

150

200

250

300

350

400

05001000150020002500300035004000

wavenumber (cm-1)

Inte

ns

ity

(5)

(4)

(3)

(2)

(1)

0 10 20 30 40 50 60

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

(9)

(8)

(7)

(6)

Inte

nsity

2 degree

sim ulated

(5)

Figure B7: The IR spectra of Frameworks 5-9

Figure B8: The powder diffraction patterns of coordination polymer (5-9) along with the simulated (black).

225

0 10 20 30 40 50 60

0

100

200

300

400

500

Inte

nsi

ty

2 degree

simulated as-synthesized catalyst recovered rxn 1 catalyst recovered rxn 2

0 10 20 30 40 50

0

100

200

300

400

500

600

Inte

nsi

ty

2 degree

simulated as-synthesized catalyst recovered rxn 1 catalyst recovered rxn 2

Figure B9: The powder diffraction patterns of catalyst 3a before and after being reacted in the Biginelli reaction at 70oC.

Figure B10: The powder diffraction patterns of catalyst 3a before and after being reacted

in the Biginelli reaction at RT for 3 days.

226

Figure B8: 119Sn-NMR spectrum of 2,6-Bis(trimethyltin)-4,8-didodecyloxybenzo[1,2-b:4,5-b’]dithiophene (34)

227

Figure B9: 119Sn-NMR spectrum of 2,6-Bis(trimethyltin)-4,8-bis(2-ethylhexyloxy)benzo

[1,2-b:4,5-b’]dithiophene (35)

228

Figure B10: 119Sn-NMR spectrum of 2,6-Bis(trimethyltin)-4,8-bis(1-ethylhexyloxy)benzo

[1,2-b:4,5-b’]dithiophene (36)

229

Figure B11: 119Sn-NMR spectrum of 2,6-Bis(trimethyltin)-4,8-bis(1-pentylhexyloxy)benzo[1,2-b:4,5-b’]dithiophene (37)

230

-5

-4.5

-4

-3.5

-3

-2.5

-2

-1.5

-1

-0.5

0

0 50 100 150 200

Temperature (oC)

Hea

t F

low

(W

/g)

0.0 0.3 0.6 0.9

-8

-6

-4

-2

0

Cu

rren

t D

en

sity

(m

A/c

m2

)

Voltage(V)

2% CN in DCB

0.0 0.5 1.0

-10

-8

-6

-4

-2

0

Cu

rren

t D

en

sity

(mA

/cm

^2)

Voltage(V)

1% CN in CB 4% CN in CB

Figure B12: Additive concentration comparison for (a) 2% CN in DCB (b) 1% and 4% CN in CB.

Figure B13: Differential Scanning Calorimetry of P13 at 20oC/min under nitrogen.

231

SPRINGER LICENSE TERMS AND CONDITIONS

Feb 25, 2011

This is a License Agreement between Christopher MacNeill ("You") and Springer ("Springer") provided by Copyright Clearance Center ("CCC"). The license consists of your order details, the terms and conditions provided by Springer, and the payment terms and conditions.

All payments must be made in full to CCC. For payment instructions, please see information listed at the bottom of this form.

License Number 2616060593670

License date Feb 25, 2011

Licensed content publisher Springer

Licensed content publication Journal of Chemical Crystallography

Licensed content title Solvothermal and Reflux Syntheses, Crystal Structure and Properties of Lanthanide-Thiophenedicarboxylate-Based Metal-Organic Frameworks

Licensed content author Christopher M. MacNeill

Licensed content date Jan 1, 2009

Volume number 40

Issue number 3

Type of Use Thesis/Dissertation

Portion Full text

Number of copies 1

Author of this Springer article Yes and you are a contributor of the new work

Order reference number

232

Title of your thesis / dissertation Synthesis Characterization and Properties of Coordination Polymers and Low Band Gap Polymers for use as Renewable Materials

Expected completion date May 2011

Estimated size(pages) 200

Total 0.00 USD

Terms and Conditions

Introduction The publisher for this copyrighted material is Springer Science + Business Media. By clicking "accept" in connection with completing this licensing transaction, you agree that the following terms and conditions apply to this transaction (along with the Billing and Payment terms and conditions established by Copyright Clearance Center, Inc. ("CCC"), at the time that you opened your Rightslink account and that are available at any time at http://myaccount.copyright.com).

Limited License With reference to your request to reprint in your thesis material on which Springer Science and Business Media control the copyright, permission is granted, free of charge, for the use indicated in your enquiry. Licenses are for one-time use only with a maximum distribution equal to the number that you identified in the licensing process.

This License includes use in an electronic form, provided it is password protected or on the university's intranet, destined to microfilming by UMI and University repository. For any other electronic use, please contact Springer at ([email protected] or [email protected])

The material can only be used for the purpose of defending your thesis, and with a maximum of 100 extra copies in paper.

Although Springer holds copyright to the material and is entitled to negotiate on rights, this license is only valid, provided permission is also obtained from the (co) author (address is given with the article/chapter) and provided it concerns original material which does not carry references to other sources (if material in question appears with credit to another source, authorization from that source is required as well). Permission free of charge on this occasion does not prejudice any rights we might have to charge for reproduction of our copyrighted material in the future.

Altering/Modifying Material: Not Permitted However figures and illustrations may be altered minimally to serve your work. Any

233

other abbreviations, additions, deletions and/or any other alterations shall be made only with prior written authorization of the author(s) and/or Springer Science + Business Media. (Please contact Springer at [email protected] or [email protected])

Reservation of Rights Springer Science + Business Media reserves all rights not specifically granted in the combination of (i) the license details provided by you and accepted in the course of this licensing transaction, (ii) these terms and conditions and (iii) CCC's Billing and Payment terms and conditions.

Copyright Notice: Please include the following copyright citation referencing the publication in which the material was originally published. Where wording is within brackets, please include verbatim. "With kind permission from Springer Science+Business Media: <book/journal title, chapter/article title, volume, year of publication, page, name(s) of author(s), figure number(s), and any original (first) copyright notice displayed with material>."

Warranties: Springer Science + Business Media makes no representations or warranties with respect to the licensed material.

Indemnity You hereby indemnify and agree to hold harmless Springer Science + Business Media and CCC, and their respective officers, directors, employees and agents, from and against any and all claims arising out of your use of the licensed material other than as specifically authorized pursuant to this license.

No Transfer of License This license is personal to you and may not be sublicensed, assigned, or transferred by you to any other person without Springer Science + Business Media's written permission.

No Amendment Except in Writing This license may not be amended except in a writing signed by both parties (or, in the case of Springer Science + Business Media, by CCC on Springer Science + Business Media's behalf).

Objection to Contrary Terms Springer Science + Business Media hereby objects to any terms contained in any purchase order, acknowledgment, check endorsement or other writing prepared by you, which terms are inconsistent with these terms and conditions or CCC's Billing and Payment terms and conditions. These terms and conditions, together with CCC's Billing and Payment terms and conditions (which are incorporated herein), comprise the entire agreement between you and Springer Science + Business Media (and CCC) concerning this licensing transaction. In the event of any conflict between your obligations

234

established by these terms and conditions and those established by CCC's Billing and Payment terms and conditions, these terms and conditions shall control.

Jurisdiction All disputes that may arise in connection with this present License, or the breach thereof, shall be settled exclusively by the country's law in which the work was originally published.

Other terms and conditions:

v1.2

Gratis licenses (referencing $0 in the Total field) are free. Please retain this printable license for your reference. No payment is required.

If you would like to pay for this license now, please remit this license along with your payment made payable to "COPYRIGHT CLEARANCE CENTER" otherwise you will be invoiced within 48 hours of the license date. Payment should be in the form of a check or money order referencing your account number and this invoice number RLNK10937838. Once you receive your invoice for this order, you may pay your invoice by credit card. Please follow instructions provided at that time. Make Payment To: Copyright Clearance Center Dept 001 P.O. Box 843006 Boston, MA 02284-3006 If you find copyrighted material related to this license will not be used and wish to cancel, please contact us referencing this license number 2616060593670 and noting the reason for cancellation. Questions? [email protected] or +1-877-622-5543 (toll free in the US) or +1-978-646-2777.

235

ELSEVIER LICENSE TERMS AND CONDITIONS

Feb 25, 2011

This is a License Agreement between Christopher MacNeill ("You") and Elsevier ("Elsevier") provided by Copyright Clearance Center ("CCC"). The license consists of your order details, the terms and conditions provided by Elsevier, and the payment terms and conditions.


Supplier Elsevier Limited The Boulevard,Langford Lane Kidlington,Oxford,OX5 1GB,UK

Registered Company Number 1982084

Customer name Christopher MacNeill

Customer address 1312 Robinhood Forest Dr

Pfafftown, NC 27040

License number 2616060986009

License date Feb 25, 2011

Licensed content publisher Elsevier

Licensed content publication Inorganica Chimica Acta

Licensed content title Synthesis, crystal structure and properties of novel isostructural two-dimensional lanthanide-based coordination polymers with 2,3,5,6-tetrafluoro-1,4-benzenedicarboxylic acid

Licensed content author Christopher M. MacNeill, Cynthia S. Day, Amy Marts, Abdessadek Lachgar, Ronald E. Noftle

Licensed content date 15 January 2011

236

Licensed content volume number 365

Licensed content issue number 1

Number of pages 8

Start Page 196

End Page 203

Type of Use reuse in a thesis/dissertation

Intended publisher of new work other

Portion full article

Format both print and electronic

Are you the author of this Elsevier article? Yes

Will you be translating? No


Title of your thesis/dissertation Synthesis Characterization and Properties of Coordination Polymers and Low Band Gap Polymers for use as Renewable Materials


Estimated size (number of pages) 200

Elsevier VAT number GB 494 6272 12

Permissions price 0.00 USD

VAT/Local Sales Tax 0.0 USD / 0.0 GBP

Total 0.00 USD

237


INTRODUCTION

1. The publisher for this copyrighted material is Elsevier. By clicking "accept" in connection with completing this licensing transaction, you agree that the following terms and conditions apply to this transaction (along with the Billing and Payment terms and conditions established by Copyright Clearance Center, Inc. ("CCC"), at the time that you opened your Rightslink account and that are available at any time at http://myaccount.copyright.com).

GENERAL TERMS

2. Elsevier hereby grants you permission to reproduce the aforementioned material subject to the terms and conditions indicated.

3. Acknowledgement: If any part of the material to be used (for example, figures) has appeared in our publication with credit or acknowledgement to another source, permission must also be sought from that source. If such permission is not obtained then that material may not be included in your publication/copies. Suitable acknowledgement to the source must be made, either as a footnote or in a reference list at the end of your publication, as follows:

“Reprinted from Publication title, Vol /edition number, Author(s), Title of article / title of chapter, Pages No., Copyright (Year), with permission from Elsevier [OR APPLICABLE SOCIETY COPYRIGHT OWNER].” Also Lancet special credit - “Reprinted from The Lancet, Vol. number, Author(s), Title of article, Pages No., Copyright (Year), with permission from Elsevier.”

4. Reproduction of this material is confined to the purpose and/or media for which permission is hereby given.

5. Altering/Modifying Material: Not Permitted. However figures and illustrations may be altered/adapted minimally to serve your work. Any other abbreviations, additions, deletions and/or any other alterations shall be made only with prior written authorization of Elsevier Ltd. (Please contact Elsevier at [email protected])

6. If the permission fee for the requested use of our material is waived in this instance, please be advised that your future requests for Elsevier materials may attract a fee.

7. Reservation of Rights: Publisher reserves all rights not specifically granted in the combination of (i) the license details provided by you and accepted in the course of this licensing transaction, (ii) these terms and conditions and (iii) CCC's Billing and Payment terms and conditions.

238

8. License Contingent Upon Payment: While you may exercise the rights licensed immediately upon issuance of the license at the end of the licensing process for the transaction, provided that you have disclosed complete and accurate details of your proposed use, no license is finally effective unless and until full payment is received from you (either by publisher or by CCC) as provided in CCC's Billing and Payment terms and conditions. If full payment is not received on a timely basis, then any license preliminarily granted shall be deemed automatically revoked and shall be void as if never granted. Further, in the event that you breach any of these terms and conditions or any of CCC's Billing and Payment terms and conditions, the license is automatically revoked and shall be void as if never granted. Use of materials as described in a revoked license, as well as any use of the materials beyond the scope of an unrevoked license, may constitute copyright infringement and publisher reserves the right to take any and all action to protect its copyright in the materials.

9. Warranties: Publisher makes no representations or warranties with respect to the licensed material.

10. Indemnity: You hereby indemnify and agree to hold harmless publisher and CCC, and their respective officers, directors, employees and agents, from and against any and all claims arising out of your use of the licensed material other than as specifically authorized pursuant to this license.

11. No Transfer of License: This license is personal to you and may not be sublicensed, assigned, or transferred by you to any other person without publisher's written permission.

12. No Amendment Except in Writing: This license may not be amended except in a writing signed by both parties (or, in the case of publisher, by CCC on publisher's behalf).

13. Objection to Contrary Terms: Publisher hereby objects to any terms contained in any purchase order, acknowledgment, check endorsement or other writing prepared by you, which terms are inconsistent with these terms and conditions or CCC's Billing and Payment terms and conditions. These terms and conditions, together with CCC's Billing and Payment terms and conditions (which are incorporated herein), comprise the entire agreement between you and publisher (and CCC) concerning this licensing transaction. In the event of any conflict between your obligations established by these terms and conditions and those established by CCC's Billing and Payment terms and conditions, these terms and conditions shall control.

14. Revocation: Elsevier or Copyright Clearance Center may deny the permissions described in this License at their sole discretion, for any reason or no reason, with a full refund payable to you. Notice of such denial will be made using the contact information provided by you. Failure to receive such notice will not alter or invalidate the denial. In no event will Elsevier or Copyright Clearance Center be responsible or liable for any costs, expenses or damage incurred by you as a result of a denial of your permission request, other than a refund of the amount(s) paid by you to Elsevier and/or Copyright Clearance Center for denied permissions.

239

LIMITED LICENSE

The following terms and conditions apply only to specific license types:

15. Translation: This permission is granted for non-exclusive world English rights only unless your license was granted for translation rights. If you licensed translation rights you may only translate this content into the languages you requested. A professional translator must perform all translations and reproduce the content word for word preserving the integrity of the article. If this license is to re-use 1 or 2 figures then permission is granted for non-exclusive world rights in all languages.

16. Website: The following terms and conditions apply to electronic reserve and author websites: Electronic reserve: If licensed material is to be posted to website, the web site is to be password-protected and made available only to bona fide students registered on a relevant course if: This license was made in connection with a course, This permission is granted for 1 year only. You may obtain a license for future website posting, All content posted to the web site must maintain the copyright information line on the bottom of each image, A hyper-text must be included to the Homepage of the journal from which you are licensing at http://www.sciencedirect.com/science/journal/xxxxx or the Elsevier homepage for books at http://www.elsevier.com , and Central Storage: This license does not include permission for a scanned version of the material to be stored in a central repository such as that provided by Heron/XanEdu.

17. Author website for journals with the following additional clauses:

All content posted to the web site must maintain the copyright information line on the bottom of each image, and he permission granted is limited to the personal version of your paper. You are not allowed to download and post the published electronic version of your article (whether PDF or HTML, proof or final version), nor may you scan the printed edition to create an electronic version, A hyper-text must be included to the Homepage of the journal from which you are licensing at http://www.sciencedirect.com/science/journal/xxxxx , As part of our normal production process, you will receive an e-mail notice when your article appears on Elsevier’s online service ScienceDirect (www.sciencedirect.com). That e-mail will include the article’s Digital Object Identifier (DOI). This number provides the electronic link to the published article and should be included in the posting of your personal version. We ask that you wait until you receive this e-mail and have the DOI to do any posting. Central Storage: This license does not include permission for a scanned version of the material to be stored in a central repository such as that provided by Heron/XanEdu.

240

18. Author website for books with the following additional clauses: Authors are permitted to place a brief summary of their work online only. A hyper-text must be included to the Elsevier homepage at http://www.elsevier.com

All content posted to the web site must maintain the copyright information line on the bottom of each image You are not allowed to download and post the published electronic version of your chapter, nor may you scan the printed edition to create an electronic version. Central Storage: This license does not include permission for a scanned version of the material to be stored in a central repository such as that provided by Heron/XanEdu.

19. Website (regular and for author): A hyper-text must be included to the Homepage of the journal from which you are licensing at http://www.sciencedirect.com/science/journal/xxxxx. or for books to the Elsevier homepage at http://www.elsevier.com

20. Thesis/Dissertation: If your license is for use in a thesis/dissertation your thesis may be submitted to your institution in either print or electronic form. Should your thesis be published commercially, please reapply for permission. These requirements include permission for the Library and Archives of Canada to supply single copies, on demand, of the complete thesis and include permission for UMI to supply single copies, on demand, of the complete thesis. Should your thesis be published commercially, please reapply for permission.

21. Other Conditions:

v1.6


If you would like to pay for this license now, please remit this license along with your payment made payable to "COPYRIGHT CLEARANCE CENTER" otherwise you will be invoiced within 48 hours of the license date. Payment should be in the form of a check or money order referencing your account number and this invoice number RLNK10937842. Once you receive your invoice for this order, you may pay your invoice by credit card. Please follow instructions provided at that time. Make Payment To: Copyright Clearance Center Dept 001

241

P.O. Box 843006 Boston, MA 02284-3006 If you find copyrighted material related to this license will not be used and wish to cancel, please contact us referencing this license number 2616060986009 and noting the reason for cancellation. Questions? [email protected] or +1-877-622-5543 (toll free in the US) or +1-978-646-2777.

242


Mar 23, 2011



Supplier

Elsevier Limited The Boulevard,Langford Lane Kidlington,Oxford,OX5 1GB,UK




Pfafftown, NC 27040


License date Mar 23, 2011


Licensed content publication Synthetic Metals

Licensed content title Synthesis, structure, and electrochemistry of N-(3-thenoyl)fluorosulfonimide and bis(2-thenoic)imide. Preparation of polymers containing the fluorosulfonimide group

Licensed content author Christopher M. MacNeill, Jian Dai, Cynthia S. Day, Stephen P. Lazar, S. Jarrett Howell, Ronald E. Noftle

243

Licensed content date August 2009

Licensed content volume number 159

Licensed content issue number 15-16

Number of pages 8

Start Page 1628

End Page 1635






Order reference number 2634890602191






VAT/Local Sales Tax 0.00 USD / GBP

Total 0.00 USD

244


INTRODUCTION


GENERAL TERMS








245








246

LIMITED LICENSE






247





21. Other Conditions: Please reapply for permission if your thesis is to be published commercially.

v1.6


If you would like to pay for this license now, please remit this license along with your payment made payable to "COPYRIGHT CLEARANCE CENTER" otherwise you will be invoiced within 48 hours of the license date. Payment should be in the form of a check or money order referencing your account number and this invoice number RLNK0. Once you receive your invoice for this order, you may pay your invoice by credit card. Please follow instructions provided at that time. Make Payment To: Copyright Clearance Center

248

Dept 001 P.O. Box 843006 Boston, MA 02284-3006 For suggestions or comments regarding this order, contact Rightslink Customer Support: [email protected] or +1-877-622-5543 (toll free in the US) or +1-978-646-2777.

249


Mar 24, 2011



Supplier Elsevier Limited The Boulevard,Langford Lane Kidlington,Oxford,OX5 1GB,UK




Pfafftown, NC 27040


License date Mar 24, 2011


Licensed content publication Synthetic Metals

Licensed content title A cyclopentadithiophene/ thienopyrrole-dione-based donor–acceptor copolymer for organic solar cells

Licensed content author Christopher M. MacNeill, Eric D. Peterson, Ronald E. Noftle, David L. Carroll, Robert C. Coffin

Licensed content date 22 March 2011

250

Licensed content volume number n/a

Licensed content issue number n/a

Number of pages 1

Start Page

End Page












VAT/Local Sales Tax 0.00 USD / GBP

Total 0.00 USD

251


INTRODUCTION


GENERAL TERMS








252








253

LIMITED LICENSE






254





21. Other Conditions: Please accept this as confirmation that, as part of your author rights, you have the right to include the journal article, in full or in part, in a thesis or dissertation. For more information on the rights you retain as a journal author, please see http://www.elsevier.com/wps/find/authorsview.authors/copyright#whatrights

v1.6


If you would like to pay for this license now, please remit this license along with your payment made payable to "COPYRIGHT CLEARANCE CENTER" otherwise you will be invoiced within 48 hours of the license date. Payment should be in the form of a check or money order referencing your account number and this invoice number RLNK0. Once you receive your invoice for this order, you may pay your invoice by credit card. Please follow instructions provided at that time.

255

Make Payment To: Copyright Clearance Center Dept 001 P.O. Box 843006 Boston, MA 02284-3006 For suggestions or comments regarding this order, contact Rightslink Customer Support: [email protected] or +1-877-622-5543 (toll free in the US) or +1-978-646-2777.

256

SCHOLASTIC VITA

Christopher M. MacNeill Born: May 28, 1983, Boston, MA, USA Education:

May 2011 Ph.D. Chemistry Wake Forest University, Winston-Salem, NC Dissertation: Synthesis, Characterization and Properties of Coordination- and Low Band-Gap Polymers for Potential Catalytic and Photovoltaic Applications Advisor: Dr. Ronald E. Noftle

August 2006 M.S. Chemistry Sacred Heart University, Fairfield, CT Magna Cum Laude

Dissertation: Synthesis, Charaterization and FT-NMR solvent effect studies on Diamagnetic Complexes of Multidentate Heterocyclic Ligands.

May 2005 B.S. Chemistry Sacred Heart University, Fairfield, CT Magna Cum Laude

Academic Experience:

2009-2010 Graduate Research Assistant Department of Chemistry, Wake Forest University 2006-2011 Graduate Teaching Assistant Department of Chemistry, Wake Forest University

Chemical Analysis I Spring 2011 Materials Chemistry I Spring 2009 Inorganic Chemistry I Fall 2010 College Chemistry I (3) Fall 2006-2008 Organic Chemistry I Spring 2007 College Chemistry II Spring 2008

257

2004-2006 Undergraduate Research Assistant

Department of Chemistry, Sacred Heart University

Professional Experience:

2005-2006 Research and Development Intern Unilever Home and Person Care, Trumbull, CT

Honors and Awards:

2007-2009 Wake Forest University Graduate Student Travel Award 2007, 2010 International Center for Materials Research Travel Award 2005-2006 Gold Medal of Excellence in Chemistry, Sacred Heart University

Publications:

“Variation of the side chain branch position leads to vastly improved molecular weight and OPV performance in 4,8-dialkoxybenzo[1,2-b:4,5-b’]dithiophene/2,1,3-benzothiadiazole copolymers.” R. C. Coffin, C. M. MacNeill, E. D. Peterson, J. W. Ward, J. W. Owen, C. A. McLellan, G. M. Smith, R. E. Noftle, O. D. Jurchescu, D. L. Carroll. J. Nanotech. 2011, accepted

“A Soluble High Molecular Weight Copolymer of Benzo[1,2-b:4,5-b’]dithiophene and Benzoxadiazole for Efficient Organic Photovoltaics.” Nie, W.; MacNeill, C.M.; Li, Y.; Noftle, R.E.; Carroll, D.L.; Coffin, R.C. Macro. Rapid Comm. 2011, submitted “A Cyclopentadithiophene/Thienopyrroledione-based Donor-Acceptor Copolymer for Organic Solar Cells.” MacNeill, C.M.; Peterson, E.D.; Noftle, R.E.; Carroll, D.L.; Coffin, R.C. Synth. Met. 2011, in press, DOI: 10.1016/j.synthmet.2011.02.010. “Synthesis, Crystal Structure and Properties of Novel Isostructural Two-Dimensional Lanthanide-Based Coordination Polymers with 2,3,5,6-Tetrafluoro-1,4-benzenedicarboxylic acid.” MacNeill, C.M.; Day, C.S.; Marts, A..; Lachgar, A.; Noftle, R.E. Inorg. Chim. Acta. 2011, 365, 196.

“Solvothermal and Reflux Syntheses, Crystal Structure and Properties of Lanthanide-Thiophenedicarboxylate-Based Metal Organic Frameworks.” MacNeill, C.M.; Day, C.S.; Gamboa, S.A.; Lachgar, A.; Noftle, R.E. J. Chem. Cryst. 2010, 40, 222.

“Synthesis, structure, and electrochemistry of N-(3-thenoyl)fluorosulfonimide and bis(2-thienoic)imide. Preparation of polymers containing the fluorosulfonimide group.” MacNeill, C.M.; Dai, J.; Howell, S.J.; Day, C.S.; Lazar, S.; Noftle, R.E. Synthetic Metals. 2009, 159, 1628.

258

“Bis(µ-dithieno[3,2-b:2',3'-d]thiophene-2,6-dicarboxylato-κ2O2:O6)bis[bis(1,10-phenanthroline-κ2N,N')cobalt(II)]dimethylformamide disolvate.” MacNeill, C.M.; Day, C.S.; Noftle, R.E. Acta Cryst., Sec. E. Cryst. Str. Rep. 2009, e65, m486.

Conference Presentations:

“Synthesis, Characterization and Photovoltaic Properties of a Series of Benzo[1,2-b:4,5-b’]dithiophene-based Conjugated Polymers for Solar Cell Applications.” Christopher M. MacNeill, Robert C. Coffin, Eric Peterson, David L. Carroll and Ronald E. Noftle; 2010 MRS Fall National Meeting, Boston, MA, United States, November 29-December 3, 2010. “A Side Chain Variation Study on a Series of Benzo[1,2-b:4,5-b’]dithiophene-Based Conjugated Polymers for Solar Cell Applications.” Christopher M. MacNeill, Robert C. Coffin, Eric Peterson, Huihui Huang, David L.Carroll and Ronald E. Noftle. ICMR Summer School on Preparative Strategies in Solid State and Materials Chemistry, University of California at Santa Barbara, Santa Barbara, CA August 8-21, 2010. “Fluorine as a Substituent in Conducting- and Coordination Polymers.” Christopher M. MacNeill, R. Eric McAnally, Abdessedek Lachgar, Ronald E. Noftle, Jian Dai, Cynthia S. Day. Department of Chemistry, Wake Forest University, Winston-Salem, NC 27106, USA. Joint 65th Northwest and 22nd Rocky Mountain Regional Meeting of the American Chemical Society, Pullman, WA, United States, June 20-23, 2010. “Catalytic Properties of Novel Lanthanide-Based Metal-Organic Frameworks Incorporating An Acidic Linker.” Christopher M. MacNeill, Cynthia S. Day, Amy Marts, Ronald E. Noftle. Department of Chemistry. Wake Forest University, Winston-Salem, NC 27106, USA. 61st Southeast Regional Meeting of the American Chemical Society, San Juan, Puerto Rico, October 21-24, 2009. “A Novel Synthesis of PTB for Application in Highly Efficient Solar Cells.” Chanitpa Khantha. Christopher M. MacNeill, Ronald E. Noftle, S. Phanichphant, David L. Carroll. Nanoscience Research Laboratory, Department of Chemistry, Chiang Mai University, Thailand. Department of Chemistry, Wake Forest University, Winston-Salem, NC 27106, USA. Center for Nanotechnology and Molecular Materials, Department of Physics, Wake Forest University, USA. Nanoconference. Bridger Field House, Winston-Salem, NC October 19, 2009. “A Two-Dimensional Metal-Organic Framework Incorporating Lanthanides and 2,3,5,6-Tetrafluoro-1,4-benzoic acid.” Christopher M. MacNeill, Cynthia S. Day and Ronald E. Noftle. Department of Chemistry, Wake Forest University, Winston-Salem, NC 27106, USA. 60th Southeast Regional Meeting of the American Chemical Society, Nashville, TN, November 12-15, 2008.

259

“Thiophene Dicarboxylates in the Synthesis of Metal-Organic Framework Materials.” Christopher M. MacNeill, Cynthia S. Day, Sergio A. Gamboa, Abdessadek Lachgar, Ronald E. Noftle. Department of Chemistry, Wake Forest University, Winston-Salem, NC 27106, USA. 4th meeting of the Materials Research Society of Africa. Dar Es Salaam, Tanzania, December 10-14, 2007

“Thiophene Dicarboxylates in the Synthesis of Metal-Organic Framework Materials.” Christopher M. MacNeill, Cynthia S. Day, Sergio A. Gamboa, Melissa Donaldson, Abdessadek Lachgar, Ronald E. Noftle. Department of Chemistry, Wake Forest University, Winston-Salem, NC 27106, USA. 59th Southeast Regional Meeting of the American Chemical Society, Greenville, SC, October 24-27, 2007.

Documents

SYNTHESIS, CHARACTERIZATION AND PROPERTIES OF … · 2014-01-17 · synthesis, characterization and properties of coordination- and low band gap polymers for potential catalytic and