Novel Calix[4]arene based Ligands:

Complexation, Extraction and Functional Materials

SEBASTIAN HAUPTRENÉ SCHNORR, STEVE ULLMANNPROF. DR. B. KERSTINGLEIPZIG UNIVERSITY

2

Working group of Prof. Dr. B. Kersting

• macrocyclic hexaaza-bis(thiophenolate) ligand

Sebastian Haupt Leipzig University

1 Kersting, B., Steinfeld, G., Fritz, T., and Hausmann, J. Eur. J. Inorg. Chem. 1999, 12, 21672 J. Lach, A . Jeremies, F. Lungwitz, B. Kersting, submitted. .

15 Å

Au(111)

• calix[4]arenes

NiNi

S S

N

N

NN

N

N

tButBu

Cl

[ClO4]

[Ni2LMe(µ-Cl)][ClO4]

3

Working group of Prof. Dr. B. Kersting

Sebastian Haupt Leipzig University

.

BMBF-project, 02NUK014C

- binding sites for alkaline and alkaline earth and/or d- and f-elements- coordination chemistry - binary interactions in liquid-liquid and solid-liquid systems

cooperation with HZDR – research site Leipzig and TU Dresden

S chadstoff

C arrier

G eom atrix/Feststo ff

++ ++

++

b inär

ternär

TU Dresden Karsten Gloe – HZDR Gert Bernhard

Steuerung des Migrationsverhaltens von Radionukliden mit Hilfe

makrozyklischer, multifunktionaler Chelatliganden

4

Introduction

• calix[4]arenes

Sebastian Haupt Leipzig University

• four conformations

OHOH HOOH OHOH

OHOH

OH

OH

OH OH OH

OH OH

OH

cone 1,3-alternatepartial-cone 1,2-alternate

1 C. D. Gutsche, M. Iqbal, Org. Synth. 1990, 68, 234–237. 2 C. D. Gutsche, Calixarenes. An introduction, RSC Publ., Cambridge, 2008.

OH OHOH HOOH

NaOH

H H

O

upper rim

lower rim

n = 4 - 14

Sebastian Haupt Leipzig University

5

Coordination chemistry of calix[4]arenes

1 S.Ullmann

• a Zn(II)-complex supported by a novel salicylidene-linked double-calix[4]arene

- CHEF-effect340 360 380 400 420 440 460 480 500 520 540 560 580 600 6200

100

200

300

400

500

600

flu

ore

sc

en

ce

inte

ns

ity

(nm)

py ex py em MeCN ex MeCN em CHCl

3 ex

CHCl3 em

OHOH OO

N

OH

N

HO

OHOH OO

H2N NH2

OHOH OO

N N

O

O

HO

Sebastian Haupt Leipzig University

6

Coordination chemistry of calix[4]arenes

1 R. Schnorr

• H2Lbandit, a calix[4]arene in partial-cone conformation

OO HOOH

O

O

O

O

O

OH O

O

O

O

H2N

O

O

OH O

O

O

O

CN

OO OO

O

O

O

OHOH OOOHOH HOOH

O

O

OH O

O

O

O

N

OH

-2:1 complexes with nitrate and chloride-2:3 complexes with acetate

• anion driven self-assembly

7

Starting point

Sebastian Haupt Leipzig University

1 Ungaro et al., J. Chem. Soc., Chem. Commun. 1984, 981. 2 Ungaro et al., J. lncl. Phen. 1984, 199.

• liquid-liquid extraction of divalent metals

OHOH OO

HO O OHO

OO OO

HO O OHOHO

OO OH

OO OO

HO O OHOO

O

O

OHOH HOOH

1 3

5 7

• focus of interest Sr2+

8

New tricks for an old dog

• systematic use of derivates

• simple CHCl3 / water system

• radiometric determination: 85Sr2+

• investigation of influences

Sebastian Haupt Leipzig University

1 S. Haupt, R. Schnorr, M. Poetsch (in preperation) 2 A. Mansel, S. Gruhne,K. Franke,S. Fischer, Production of 85Sr at a 18 MeV-cyclotron and purification for geochemical investigations 2012 (Submitted )

OHOH OO

R1 R1R1 R1

O

1 R1 = H, R2 = Me2 R1 = H, R2 = OEt3 R1 = H, R2 = OH4 R1 = tBu, R2 = Me5 R1 = tBu, R2 = OEt6 R1 = tBu, R2 = OH

R2 O R2

1 2 3 4 5 6

05

1015202530

5.56.57.58.5

compound

extr

act

ion

of

Sr2

+

[%]

• pH value, counter ion, temperature, time, concentration

- pH = 9- 1 h shaking- room temperature- ligand/strontium 5/1

over 95 % extractedstrontium

9

Synthetic groundwater

Sebastian Haupt Leipzig University

1 P. Mell et al. Journal of Radioanalytical and Nuclear Chemistry 2006, 268, 405-410.2 B. Torstenfelt, K. Andersson, B. Allard Chemical Geology 1982, 36, 123-137.

ionconcentration /

µmol/L

HCO3- 1445.5

SO42- 120.4

Cl- 0.9

NO3- 3.9

F- 15.3

HPO42- 69.8

Na+ 1480.4

K+ 86.6

Ca2+ 0.3

Mg2+ 0.2

Al3+ 398.8

Fe3+ 11.7

Mn2+ 2.8

Ba2+ 64.4

Sr2+ 719.0

Ca2+

Fe3+

Al3+

Na+Ba2

+

phos

phat

e

sulfa

te

carb

onat

e0

20

40

60

80

100

3E-6M

3E-5M

3E-4M

inorganic impurities

extr

act

ion o

f S

r2+

[%

]

citric

acid

tarta

ric a

cid

oxalic

acid

urea

asco

rbic

acid

met

hion

ine

EDTA

020406080

100

3E-6M

3E-5M

3E-4M

organic impurities

extr

act

ion o

f S

r2+

[%

]

over 90 % extractedstrontium

OHOH OO

HO O OHO

Sebastian Haupt Leipzig University

10

Immobilization on mesoporous CPG-silica

SiO

O On

OHOH HOOH

SiO2calix[4]arenejoint linker

solid support

joint-triazole, tetrazole-ester, amino acid-imine, amine-ether-C-C coupling

SiO

O On SiO2

HSc[4]a

radical thiol addition

1 R. Brindle, K. Albert, J. D. Glennon, Journal of Chromatography A 1996, 731, 41–46. 2 J. D. Glennon, E. Horne, K. Hall, D. Cocker, M. A. McKervey, Journal of Chromatography A 1996, 731, 47–55.

SiO

O On SiO2

Sc[4]a

Sebastian Haupt Leipzig University

11

OHOH HOO OHOH OOH

OO

OHOH OO

OOO O

OHOH OO

OHOO OH

HS SiO

S SiO

OHOH OO

OHOO OH

1 4 5 6

7

CPG-SH

SiO2O

O

SiO2O

OSiO2

HO

HO

CPG-S-7

CPG

Immobilization on mesoporous CPG-silica

1 S. Haupt, M. Handke (in preparation)

OHOH HOOH OHOH OO

OOO O

OHOH OO

OOO O

OHOH HOO

1 2 3a 3b

Sebastian Haupt Leipzig University

12

Immobilization on mesoporous CPG-silica

O OH O

OHOOHO

S SiO

OO

SiO2

14

1312

1119

9

8

1a2a

3a4a

1b

2b

3b

4b

1c

2c

3c

4c5a 5b

7

6

• 13C CP/MAS NMR

• DTA thermal stability to 300 °C

• elemental analyses up to 0.5 mmol ligand / g CPG

• Raman no SH vibration

13

Solid-liquid-extraction

Sebastian Haupt Leipzig University

1 M. Poetsch

• batch experiments

Sr2+

SSE

S SiO

OHOH OO

OHOO OH

SiO2O

O

CPG-S-7

strontium saltbuffer, ph = 9

filtrationgammacounter

compound CPG CPG-S-c[4]a CPG-S-7

extraction of Sr2+ [%] < 5 10 – 20 > 90

14

Posters

• see poster number 6 and 28

Sebastian Haupt Leipzig University

1 A. Jeremies, R. Schnitter, M. Börner

NiNi

S S

N

N

NN

N

N

tButBu

Cl

[ClO4]

[Ni2LMe(µ-Cl)][ClO4]

SH

N

N

N

N

HS

N

N

tBu tBua) M-salt

b) LiClO4

encapsulation of amino acids gold nanoparticles

Thank you for your attention.

Das diesem Vortrag zugrundeliegende Vorhaben wurde mit Mitteln des Bundesministeriums für Bildung

und Forschung unter dem Förderkennzeichen 02NUK014C gefördert.

Sebastian Haupt Leipzig University

16

Anhang

HO

HO

O

O

HO

O

O

O

O

O

OH

OH

Sr

O

O

OH

O

B

OHHO OO

O O OOSr

A

-5,0 -4,5 -4,0 -3,5 -3,0-1,5

-1,0

-0,5

0,0

0,5

1,0

1,5

2,0

2,5

3,0 log D Linear Fit log D

log

D

log [L]

Sebastian Haupt Leipzig University

17

Anhang

CPG-SiO2: OF ~ 100m2/g, Porengröße 30nm (groß), Körnung 100-400µm, OH-dichte 4-6/nm2 max 1 mmol OH/g (mit 6 OH gerechnet)