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This is a presentation of my graduate research towards my Ph.D. in Chemistry. I studied how changing the structure of a polymer changed its light absorption and emitting properties, and subsequently, its ability to transfer energy to other species, namely lanthanide complexes of europium and erbium. This research was focused on developing methods to increase efficiencies of light-emitting materials by tuning energy levels of the donor and acceptor species.
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Design and Syntheses of Polymeric Materials for Visible and Near-Infrared Emitting Applications
Sean Owen Clancy, Ph.D.
POLYMER LIGAND Eu+3
ET - Dexter
ET - Förster
S1
T1
S0
S1
T1
S0 7F2
5D0
5D2
All material contained within is copyright © 2006 Sean Owen Clancy and / or the respective institutions.
Polymeric Energy Transfer Complexes
O
O
ArylLn
L
L
C10H21O
OC10H21
n
N
N NLn
LL
L
C10H21O
OC10H21
n
O
O
Aryl
N
Er
N
N
N
C10H21O
OC10H21
n
• PM_aryl:Ln(L)2
• PM_trp:Ln(L)3
• PM_aryl:ErTPP
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Graduate Research Overview• Background
• Harper Group Research • Research Goals and Motivation• Recent Applications• Lanthanides• Ligands• Color Tuning• Polymers Photophysics• Energy Transfer
• Visible Emission Resulting from Energy Transfer from Polymers to Ligands to Europium• Polymers with Pendant Terpyridines• Polymers with Pendant β-Diketonates
• Infrared Emission Resulting from Energy Transfer from Polymers to Ligands to Erbium
• Summary
• Future Work
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Harper Group Research
• Energy Transfer Studies• Light Harvesting Dendrimers• Light Harvesting Polymers• Polymer Photophysics
• Lanthanide Complexes• β-Diketonate Ligands• Dative Bonding Heterocyclic Ligands
• Photonic Materials• Lanthanide Containing Materials• Organometallic Systems• PPV Syntheses• Polymer Sensors• Photonic Crystals• Quantum Dots• Two-Photon Dyes
N N
O
O
S
EuN
N
3
N N
OC10H21
C10H21On
N
N
N
n
• Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Research Goals and MotivationFacilitate Tunability and Processing• Polymers are easier to process than inorganic systems.• Polymeric device properties can be altered by changing the chemical structure of the
polymer.
Increase Efficiencies• Electrical excitation produces 25% singlets and 75% triplets.1• Polymeric devices typically have higher external quantum efficiencies than small
molecule devices.2,3
• Electrophosphorescent devices have higher efficiencies than electroluminescent devices.4
• Lanthanides exert the “heavy atom effect,” creating more triplet states,5 which the lanthanides can harvest and emit as pure colors.
• Improve efficiencies by bringing the donors and acceptors closer to each other.• Increase dopant/acceptor concentration and prevent aggregation as well.
1. Brown, A. R.; Pichler, K.; Greenham, N. C.; Bradley, D. D.; Friend, R. H.; Holmes, A. B. Chem. Phys. Lett., 1993, 210, 61.2. Baldo, M. A.; O'Brien, D. F.; Thompson, M. E.; Forrest, S. R. Phys. Rev. B, 1999, 60, 14422.3. Wilson, J. S.; Dhoot, A. S.; Seeley, A. J. A. B.; Khan, M. S.; Kohler, A.; Friend, R. H. Nature, 2001, 413, 828.4. Baldo, M.A.; Lamansky, S.; Burrows, P.E.; Thompson, M.E.; Forrest, S.R. Appl. Phys. Lett., 1999, 75, 4.5. Mukherjee, K. K. R. Fundamentals of Photochemistry, Wiley Eastern Ltd. India, 1992.
• Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Background – Recent Applications• Conjugated polymers have many applications:
• Photovoltaics
• OLEDs
Flexible photovoltaic diode http://www.oc.chalmers.se/science/konjug_polymerer.htm
20” OLED full color display by IBM 2002.http://www.zurich.ibm.com/st/display/demo.html
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Kodak EasyShare Digital CameraActive-matrix OLEDhttp://www.kodak.com/go/display/
Background – Lanthanides• Pure color emission (shielded f orbital transitions)• Robust metals (will not photobleach)• Induce heavy atom effect (improves rate of intersystem crossing)• Triplet harvesters• Reduce polymer degradation
• Eu+3, Sm+3, and Tb+3 can be used in visible devices• Er+3 can be used in EDFA (1.55 mm)• Nd+3 and Yb+3 can be used in IR-emitting devices
• Direct excitation is inefficient, to overcome• Laser source• Ligands
• Energy transfer is important• Conjugated organic ligands allow for ET• Ligands shield lanthanide ion from external environment, such as solvent (mode of energy loss) and other lanthanide ions (self quenching).
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Background – Ligands
• Lanthanides have a high number of coordination sites (from six to twelve).• Their f orbitals are unable to form hybrid orbitals with ligand.• Need ligands to bind with more than one coordination site (multidentate).• Dative bonding ligands, such as terpyridine:
• Bidentate ligands, such as beta-diketonates, form both covalent and dative bonds:
NN
N
R1
O OH
R3R2
R1
O O
R3R2
• Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Background – Color Tuning• PPV and PPP type polymers are widely used
R
R
R
R R RPFPPP PPV
N N
PPy PPyV
n n n nn
• Mechanical properties- Light weight, easy to process
• Infinite π-system• Give rise to a band structure• Band gap varies according to
structure
http://www.tn.utwente.nl/cms/polymers/conj_pol.htm
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Background – Polymer Photophysics
a b c
d
e
f
g
h
S0
S1
T1
Energy level diagram showing modes of deactivation:
• a – absorbance
• b – fluorescence
• c – nonradiative decay
• d – intersystem crossing
• e – singlet energy transfer
• f – triplet energy transfer
• g – phosphorescence
• h – internal crossing
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Background – Energy Transfer
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Forster Energy Transfer
• Singlet to singlet• Coupled dipole-dipole interaction; through space
Dexter Energy Transfer
• Triplet to triplet• Exchange mechanism; through bond
D* A D A*
D* A D A*
Background – Energy Transfer Polymer to Ligand to Lanthanide
PO LY M ER LIG A N D Eu+3
ET - D exter
ET - Förster
S 1
T1
S 0
S 1
T1
S 0 7F2
5D 0
5D 2
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Sensitization of Europium Chelates
Design and Synthesis of β-Diketone Ligands
S
OO
Ar
S
BTM DTM 3-PTM 9-PTM
Ar =
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Sensitization of Europium ChelatesLigand Structures
BTM DTM 3-PTM 9-PTMHFA
S
O
O
S
CF3
O
O
CF3
S
O
O
S
O
O
S
O
O
Asymmetric –Extent of Conjugation LengthAsymmetric Vs. Symmetric
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
• Asymmetric ligands perturb the ligand field around a lanthanide.• The more asymmetric the field, the greater the lanthanide’s emission intensity.
• Shorter effective conjugation length increases the energies of a ligand.• Larger energy gap will reduce the possibility for back energy transfer.
• Minimizes a pathway for energy loss.
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Sensitization of Europium ChelatesLigand Syntheses
S
O
S
O
S
O
O
S
O
O
S
O O
S
S
O O
S
O O
S
O O
O
O
O
O
S
O
O
NaH
THF
NaH
THF
NaH
THF
NaH
THF
BTM
DTM
3-PTM
9-PTM
Sensitization of Europium ChelatesPolymer Structures
O
O
ArylLn
L
L
C10H21O
OC10H21
N
N NLn
LL
L
C10H21O
OC10H21S
O
N
N
N
n n
Polymer Aryl Group
PM_th
PM_fu
PM_py
PM_pz
PM_trp
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Sensitization of Europium ChelatesEnergy Level Tuning of Polyphenylenes – Primary Donors
The synthetic route to PM_es and P1 (i.) ethanol/ PTSA refluxed 24hrs; (ii.) Pd(PPh3)4, 2M Na2CO3, toluene, refluxed 72hrs).
(HO)2B B(OH)2
C10H21O
OC10H21
Br Br
COOH
Br Br
O O C10H21O
OC10H21
O O
n
i ii
(HO)2B B(OH)2
C10H21O
OC10H21
Br BrC10H21O
OC10H21
n
ii
PM_es
P1
+
+
Photophysical properties of P1 and PM_es in THF.EmissionPolymers Abs. Max
(nm) Max(nm)
FWHM(nm)
φFL τ(ns)
P1 350 411 61.5 0.386 0.690 3.24 2.31
PM_es 330 392 61.5 0.662 1.665 3.41 2.47
Singlet energy(eV)
Triplet energy(eV)
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Sensitization of Europium Chelates
Synthesis of Polymers with Pendant TerpyridinesBound to Europium(III) β-Diketonates
N
N NLn
LL
L
C10H21O
OC10H21
n
PM_trp
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Polymer with Terpyridines Synthesis
OH
OH
OC10H21
OC10H21
OC10H21
OC10H21
Br
Br
C10H21O
OC10H21
(HO)2B B(OH)2
Br-C10H21
K2CO3CH3CN
Br2
CH3Cl
n-Butyllithium
THFB(OMe)3
N
O
N
O
N+
I-
I2
N
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Polymer with Terpyridines Synthesis
Br Br
CHO
NO
N NO
Br
Br
N
O
I-Br Br
NN
N
+
KOH
MeOHNH4OAc
MeOH
OC10H21
C10H21O
NN N
n
OC10H21
C10H21O
Br
NN N
(HO)2B B(OH)2
Br
PM_trp
Pd(PPh3)4
K2CO3, THF+
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Polymer-Lanthanide Chelate Synthesis
OC10H21
C10H21O
NN N
n
O O
R2R1
3 eq NaOEt, 1 eq LnCl3
THF
3 eq
OC10H21
C10H21O
NN N
n
O O
R2R1
Ln
3
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Sensitization of Europium Chelates
Materials Characterization and Photophysical Performance Data
PM_trp
N
N NLn
LL
L
C10H21O
OC10H21
n
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Polymer with Terpyridines CharacterizationPolymer molecular weights were determined by gel permeation chromatography (GPC) and multiple angle laser light scattering (MALLS).
Polymer dn/dc (mL/g) Mn (g/mol) Mw (g/mol) PDI
PM_trp 0.1608 8.669 x 106 1.117 x 107 1.29
Photophysical properties of polymers PM_trp in THF.
PM_trp
Absorption maximum 320 nm
Fluorescence maximum 416 nm
FWHM 85 nm
Stokes’ shift 7,212 cm-1
ΦFL 0.062
Lifetime (weighting coefficient) 0.27 ns (0.60)1.49 ns (0.40)
Singlet energy level (ES) 3.32 eV
Triplet energy level (ET) 2.47 eV
Singlet-triplet gap (∆EST) 0.85 eV
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Polymer with Terpyridines Characterization
300 350 400 450 500 550 600
0.0
0.2
0.4
0.6
0.8
1.0
1.2
PM_trp abs PM_trp ems
N
orm
aliz
ed in
tens
ity
Wavelength (nm)
The absorbance and emission spectra of polymer PM_trp in THF (ex = 320 nm).
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
PM_trp:Eu(L)3 Emission Spectra
325 350 375 400 425 450 475 500 525 550 575 600 625
0.0
2.0x105
4.0x105
Excited @ Poly Abs Max
PM_trp:Eu(BTM)3 PM_trp:Eu(DTM)3 PM_trp:Eu(3-PTM)3 PM_trp:Eu(9-PTM)3
Inte
nsity
(Cou
nts)
Wavelength (nm)
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
PM_trp:Eu(L)3 Emission Maxima
1 2 3 45.0x104
1.0x105
1.5x105
2.0x105
2.5x105
3.0x105
3.5x105
4.0x105
PM_trp:Eu(L)3 Emissions, where Ligands:1 = BTM, 2 = DTM, 3 = 3-PTM, 4 = 9-PTM
Residual Emission Europium Emission
Inte
nsity
Ligands
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
PM_th:Eu(L)2 Ligands Versus Energy Parameters
0
0.2
0.4
0.6
0.8
1
1.2
1 2 3 4
Ligands
Nor
mal
ized
Uni
ts
Emission Intensity DScm-1 DTcm-1
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
PM_trp:Ln(L)3 Systems, where Ligands: 1 = BTM, 2 = DTM, 3 = 3-PTM, 4 = 9-PTM.
∆S
• Smaller distances in singlet energies (∆S) from polymer to polymer-ligand complexes inversely relate to greater emission intensities from complexes.• Suggests Forster ET of greater significance than Dexter ET for polymer to ligand ET.
∆T
PM_th:Eu(L)2 Ligands Versus Energy Parameters
PM_trp:Ln(L)3 Systems, where Ligands: 1 = BTM, 2 = DTM, 3 = 3-PTM, 4 = 9-PTM.
0.70.750.8
0.850.9
0.951
1.05
1 2 3 4
Ligands
Norm
aliz
ed U
nits
DEST∆EST
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
• Greater distances in singlet to triplet energies for polymer-ligand complexes almost directly relate to greater emission intensities from complexes.• Suggests back energy transfer led to lower emission intensities for DTM and 3-PTM.
• Forward ISC favored by BTM and 9-PTM.
PM_trp:Ln(L)3 Systems CharacterizationPhotophysical properties of PM_trp gadolinium complexes.
PM_trp:Gd(HFA)3
PM_trp:Gd(BTM)3
PM_trp:Gd(DTM)3
PM_trp:Gd(3-PTM)3
PM_trp:Gd(9-PTM)3
Abs. Max (nm)(cm-1)
31731,546
35827,933
37426,738
37626,596
35827,933
Em. Max (nm)(cm-1)
40025,000
41024,390
42323,641
42923,310
41024,390
∆ (cm-1) 6,546 3,543 3,097 3,286 3,543
ES (eV)(cm-1)
3.4027,397
3.2125,907
3.0924,938
3.0724,722
3.2025,773
ET (eV)(cm-1)
2.7622,297
2.4619,841
2.4319,608
2.4820,000
2.4519,763
∆EST (eV) 0.64 0.75 0.66 0.59 0.75
Energy transfer efficiencies from PM_trp to L in PM_trp:Eu(L)3 systems, where L = BTM, DTM, 3-PTM, and 9-PTM.
BTM DTM 3-PTM 9-PTM
PM_trp:Eu(L)3 0.993 0.994 0.991 0.993
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
PM_trp:Ln(L)3 Systems CharacterizationThe energy transfer mechanism for the PM_trp:Eu(BTM)3 system.
3.21
2.46 2.46
3.40
2.76
Eu+3 BTM Polymer PM_trp BTM Eu+3
2.14
2.36
2.64
2.14
2.36
2.64
FÖRSTERMECHANISM
DEXTERMECHANISM
a
b
cd
e
f
h
i
g
Energy (eV)
h
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Sensitization of Europium Chelates
Synthesis of Polymers with Pendant β-DiketonatesBound to Europium(III) β-Diketonates
O
O
ArylLn
L
L
C10H21O
OC10H21S
O
N
N
N
n
Polymer Aryl Group
PM_th
PM_fu
PM_py
PM_pz
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Polymers with β-Diketonates Synthesis
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Br Br
O OH
Br Br
O O
PTSA
EtOH
OC10H21
C10H21O
(HO)2B B(OH)2
Br Br
O O
Pd(PPh3)4, THF
KCO3 (aq.)
O O
OC10H21
C10H21On
O O
OC10H21
C10H21On
SONaH
THF
O
O
OC10H21
C10H21O
n
S
PM_es
PM_th
Polymer-Lanthanide Chelate Synthesis
O
O
OC10H21
C10H21O
n
Ar
O
O
OC10H21
C10H21O
n
Ar
O O
R2R1
O
O
R2
R1 Ln
2
3 eq NaOEt, 1 eq LnCl3
THF
2 eq
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Sensitization of Europium Chelates
Materials Characterization and Photophysical Performance Data
O
O
ArylLn
L
L
C10H21O
OC10H21S
O
N
N
N
n
Polymer Aryl Group
PM_th
PM_fu
PM_py
PM_pz
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Polymers with β-Diketonates CharacterizationPolymer molecular weights determined by GPC and MALLS in CHCl3.
Polymer dn/dcmL/g
Mng/mol
Mwg/mol
DP PDI
PM_es 0.0975 1.27x104 1.64x104 24 1.28
Photophysical properties polymers with β-diketonate pendant groups.
PM_th PM_fu PM_py PM_pz
Abs. Max (nm)(cm-1)
33030,300
33230,120
33030,300
33030,300
Em. Max (nm) (cm-1)
396.525,220
39125,575
39125,575
39625,250
FWHM (nm) 59 54 54.5 58.4
∆ (cm-1) 5,082 4,545 4,728 5,051
QE 0.2121 0.2154 0.1915 0.2134
Life Times (ns) 1.65 1.66 1.52 1.68
kf (s-1) 1.32 x 108 1.32 x 108 1.26 x 108 1.27 x 108
kST (s-1) 4.74 x 108 4.72 x 108 5.31 x 108 4.68 x 108
ES (eV)(cm-1)
3.4027,425
3.4027,425
3.4227,585
3.4027,425
ET (eV)(cm-1)
2.5020,165
2.5020,165
2.5020,165
2.4719,920
∆EST (eV) 0.90 0.90 0.92 0.93
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
350 375 400 425 450 475 500 525 550 575 600 625 650
0
1x105
2x105
3x105
4x105
5x105
6x105
Excited @ Poly Abs Max
PM_th:Eu(BTM)2 PM_th:Eu(DTM)2 PM_th:Eu(3-PTM)2 PM_th:Eu(9-PTM)2
Inte
nsity
(cou
nts)
Wavelength (nm)
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
PM_th:Eu(L)2 Emission Spectra
1 2 3 40
1x105
2x105
3x105
4x105
5x105
6x105 PM_th:Eu(L)2 Emissions, where Ligands:1 = BTM, 2 = DTM, 3 = 3-PTM, 4 = 9-PTM
Residual Emission Europium Emission
Inte
nsity
(cou
nts)
Ligand
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
PM_th:Eu(L)2 Emission Maxima
PM_th:Eu(L)2 Ligands Versus Energy Parameters
0
0.2
0.4
0.6
0.8
1
1.2
1 2 3 4
Ligands
Nor
mal
ized
Uni
ts
Emission Intensity DScm-1 DTcm-1
PM_th:Ln(L)2 Systems, where Ligands: 1 = BTM, 2 = DTM, 3 = 3-PTM, 4 = 9-PTM.
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
∆S
• Smaller distances in singlet energies (∆S) from polymer to polymer-ligand complexes inversely relate to greater emission intensities from complexes.• Suggests Forster ET of greater significance than Dexter ET for polymer to ligand ET.
∆T
PM_th:Eu(L)2 Ligands Versus Energy Parameters
0.75
0.8
0.85
0.9
0.95
1
1.05
1 2 3 4
Ligands
Nor
mal
ized
Uni
ts
DEST
PM_th:Ln(L)2 Systems, where Ligands: 1 = BTM, 2 = DTM, 3 = 3-PTM, 4 = 9-PTM.
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
∆EST
• Greater distances in singlet to triplet energies for polymer-ligand complexes almost directly relate to greater emission intensities from complexes.• Suggests back energy transfer led to lower emission intensities for DTM and 3-PTM.
• Forward ISC favored for BTM and 9-PTM.
PM_th:Ln(L)2 Systems CharacterizationPhotophysical properties of PM_th gadolinium complexes.
PM_th:Gd(HFA)2
PM_th:Gd(BTM)2
PM_th:Gd(DTM)2
PM_th:Gd(3-PTM)2
PM_th:Gd(9-PTM)2
Abs. Max (nm)(cm-1)
33130,211
35827,933
37426,738
37826,455
35827,933
Em. Max (nm)(cm-1)
39125,575
41624,038
42123,753
42723,419
40524,691
∆ (cm-1) 4,636 3,895 2,985 3,036 3,242
ES (eV)(cm-1)
3.4227,548
3.2326,042
3.0924,876
3.0624,691
3.2125,907
ET (eV)(cm-1)
2.7522,148
2.4219,531
2.3819,231
2.4019,380
2.3919,305
∆EST (eV) 0.67 0.81 0.71 0.66 0.82
Energy Transfer Efficiencies from Polymer to Ligand to PM_aryl:Eu(L)2 Systems, where L = HFA, BTM, DTM, 3-PTM, or 9-PTM.
BTM DTM 3-PTM 9-PTM
PM_fu:Eu(L)2 0.998 0.998 0.998 0.998
PM_py:Eu(L)2 0.999 0.998 0.998 0.998
PM_pz:Eu(L)2 0.998 0.998 0.997 0.998
PM_th:Eu(L)2 0.998 0.998 0.998 0.998
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
PM_th:Ln(L)2 Systems CharacterizationThe energy transfer mechanism for the PM_th:Eu(BTM)2 system.
3.23
2.42 2.42
3.42
2.75
Eu+3 BTM Polymer PM_th BTM Eu+3
2.14
2.36
2.64
2.14
2.36
2.64
FÖRSTERMECHANISM
DEXTERMECHANISM
a
b
cd
e
f
h
i
g
Energy (eV)
h
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Conclusions – Europium Sensitization Project• Energy transfer has been shown to occur from polyphenylenes as the energy donors to ligand systems as intermediate acceptors and then to lanthanides as the terminal acceptors.
• Higher intensities of emission from lanthanide were due to:• Ligands that were asymmetric and had shorter effective conjugation lengths.• Binding acceptor complex directly to donor polymer.
• Pendant β-diketonates bind complex better than terpyridines.• Better matching of energy levels between ligand systems with lanthanides, as illustrated by BTM and 9-PTM being brighter than DTM and 3-PTM.
• Smaller relative singlet energy distances between polymer and polymer-ligandsystem (favoring Forster ET).• Larger relative singlet to triplet energy gaps on polymer-ligand systems (favoring forward ISC).
Applications• Organic / Polymer Light Emitting Diodes• Methods of Optimizing O/PLEDs• Sensors
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Sensitization of Erbium Chelates
Synthesis of Polymers with Pendant β-DiketonatesBound to Erbium(III) meso-Tetraphenylporphyrinate
S
O
N
N
N
O
O
Aryl
N
Er
N
N
N
C10H21O
OC10H21
n
Polymer Aryl Group
PM_th
PM_fu
PM_py
PM_pz
Erbium Porphyrinate Synthesis
N
N
HNNHN
N NN
Li
Li
OO
OO
NN N
N
Er
Cl
O
O
LiN
SiSi
CH3
CH3
CH3
H3C
H3CCH3
DME
ErCl3
Toluene
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Verified with x-ray crystal.
Polymer Erbium Chelate Synthesis
NN N
N
Er
Cl
O
O
O
O
OC10H21
C10H21O
n
S
O
O
N
N
N
N
ErS
n
NaOEt / EtOH
THF
C10H21O
OC10H21
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Sensitization of Erbium Chelates
Photophysical Performance Data
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
S
O
N
N
N
O
O
Aryl
N
Er
N
N
N
C10H21O
OC10H21
n
Polymer Aryl Group
PM_th
PM_fu
PM_py
PM_pz
300 400 500 600 700-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8 Cl(DME)ErTPP PM_th:ErTPP PM_fu:ErTPP PM_py:ErTPP PM_pz:ErTPP
Abs
orba
nce
Wavelength (nm)
Poly:ErTPP Absorbance Spectra
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
325 350 375 400 425 450 475 500 525 550
0.0
5.0x106
1.0x107
1.5x107
2.0x107
2.5x107
3.0x107
PM_th - Exc(323) Cl(DME)ErTPP - Exc(323) PM_th:ErTPP - Exc(323)
Inte
nsity
(cou
nts)
Wavelength (nm)
PM_th:ErTPP Visible EmissionExciting @ Poly Max, Relative to PM_th and Cl(DME)ErTPP
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
1400 1450 1500 1550 1600 1650 1700
3.0x104
3.1x104
3.2x104
3.3x104
3.4x104
3.5x104
3.6x104
3.7x104
3.8x104
3.9x104
4.0x104
4.1x104
4.2x104
4.3x104 Cl(DME)ErTPP - Exc(422) PM_th:ErTPP - Exc(424) PM_fu:ErTPP - Exc(424) PM_py:ErTPP - Exc(422) PM_pz:ErTPP - Exc(424)
Inte
nsity
(cou
nts)
Wavelength (nm)
Poly:ErTPP Infrared EmissionExciting at Porphyrin Absorbance Maxima
Room temperature IR emission at 10-5 M in degassed, anhydrous THF.
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Poly:ErTPP Infrared EmissionExciting at Polymer Absorbance Maxima
1400 1450 1500 1550 1600 1650 1700
4.6x104
4.8x104
5.0x104
5.2x104
5.4x104
5.6x104 PM_th:ErTPP - Exc(323) PM_fu:ErTPP - Exc(323) PM_py:ErTPP - Exc(323) PM_pz:ErTPP - Exc(323)
Inte
nsity
(cou
nts)
Wavelength (nm)
Room temperature IR emission at 10-5 M in degassed, anhydrous THF.
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Conclusions – Erbium Sensitization Project
• Energy transfer has been shown to occur from polyphenylenes as the energy donors to a porphyrin system as an intermediate acceptor and then to erbium as the terminal acceptors.
• Infrared emission from a room temperature solution was shown.
• Intensity of erbium emission indifferent to aryl group identity on beta-diketonate.
• Erbium emission ~33% more intense when excited at porphyrin absorbance max.
• Suggests less than ideal matching of energy levels between polymer and porphyrin ligand.
• Either need to modify polymer to match ligand or modify ligand to match polymer.
• Opportunity to provide higher doping densities when coordinating to polymer.
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Summary
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
• Design and synthesis of polymers with higher singlet and triplet energies.• Kink introduced with para-meta alternation increased both singlet and triplet energy levels of polyphenylene polymers.
• Design and synthesis of europium complexes with lower triplet energies.• Changing the structure of one of the aryl groups on a β-diketonate results in predictable photophysical changes.
• Shorter conjugation length and higher asymmetry results in higher intensity of lanthanide emission.
• Higher intensity of lanthanide emission produced though the smaller relative singlet energy distances between polymer and polymer-ligand system (favoring Forster ET) and larger relative singlet to triplet energy gaps on polymer-ligand systems (favoring forward ISC).
• Design and synthesis of polymers with the ability to coordinate to lanthanides.• Polyphenylene-based polymers with pendant ligand functional groups in the repeat unit are able to donate energy to lanthanide complexes.
• Europium systems produced visible emission.• Erbium systems produced infrared emission.
Future Work
Extending this Research• Isolating the final complexes and characterizing by crystal structures or other means.
• Most likely to include model compounds of dimers or trimers of the monomer unit.
• Incorporating these materials into devices and analyzing their performance.
• See if Dexter ET becomes favored via electrophosphosphorescence, since more triplets should be formed.
• IR-emitting displays for reading while wearing night-vision goggles.
• IR-emitting materials for waveguides and other telecommunication devices.
• Polymer-bound iridium systems for LEDs and related devices.
• Sensors for a variety of analytes: biologicals, inorganics, and organics.
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Knowledge, Skills, and AbilitiesEnhanced or Obtained via this Research
• Design and synthesis of: small molecule organics, organometallic complexes / coordination complexes, and polymers.
• Characterization of materials through a variety of techniques: NMR, mass spectrometry, elemental analysis, x-ray crystallography, absorption spectroscopy, fluorescence and phosphorescence spectroscopy, etc..
• Purification of materials via: column chromatography, preparative thin layer chromatography, medium pressure chromatography, ambient pressure and vacuum distillation, reprecipitation, recrystallization, and sublimation.
• Structure-property / structure-function relationship studies.
• Data analysis using a variety of software: Excel, Igor Pro, Origin, PhotoChemCAD, etc..
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California
Acknowledgements
University of Southern CaliforniaResearch Adviser Harper Research GroupAaron W. Harper, Ph.D. Patrick J. Case, Ph.D.
Jeremy C. Collette, Ph.D.Committee Members Michael D. Julian, Ph.D.William P. Weber, Ph.D. Cory G. Miller, Ph.D.William H. Steier, Ph.D. Asanga B. Padmaperuma, Ph.D.
Funding was provided by:• A MURI grant administered by the Air Force Office of Scientific Research (contract number 413009) and • A PECASE grant administered by the Army Research Office (contract number DAAD 19-01-1-0788). • Harold G. Moulton Fellowship, Benson Endowed Fellowship, USC, and LHI.
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California