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Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains

Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains
Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains
A series of conjugated triaryl compounds have been synthesized, consisting of thiophene or selenophene peripheral units and a central 1,3,4-thiadiazole (TDA) heterocycle. X-ray crystallographic studies on four of the materials reveal that the molecules are planar in the solid state and feature an array of intramolecular (heteroatomic) and intermolecular (heteroatomic and -) noncovalent close contacts. Electrochemical oxidative polymerization affords insoluble polymers for EDOT-TDA-EDOT and EDTT-TDA-EDTT. The band gaps of the polymers have been deduced by cyclic voltammetry and electronic absorption spectroscopy and were found to be 1.8-1.9 eV. Both polymers show good stability toward n-doping and the EDTT analogue is more readily reduced than the EDOT-containing system. The enhanced stability toward n-doping, compared with the homopolymers PEDTT and PEDOT, is attributed to the presence of the electron deficient thiadiazole unit. The LUMO of poly(EDTT-TDA-EDTT) is 0.3 eV lower than that of poly(EDOT-TDA-EDOT), demonstrating that the substituent effect of the chalcogen atom is an important contributor to the electronic properties of the polymers.
thiophene, optical-properties, intramolecular charge-transfer, substituted polythiophenes, pi-conjugated, polymers, donor, narrow-bandgap, field-effect transistors, oligomers, copolymers
6585-6593
Pang, H.
39293079-a9b8-466e-99b1-b635ebee30a3
Skabara, P.J.
4479c8a5-753f-4735-9c19-c057bb2c6a5e
Crouch, D.J.
f41dfdde-862f-4263-bc99-2b2cfd8bd35e
Duffy, W.
1d7dbfd0-fadf-4232-8ae8-1da1475edbe0
Heeney, M.
50a620f3-51c5-4d5f-9e53-9bbf06636a5f
McCulloch, I.
7bf7b885-809e-4371-8afa-0a3de08a9b5e
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horton, P.N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Pang, H.
39293079-a9b8-466e-99b1-b635ebee30a3
Skabara, P.J.
4479c8a5-753f-4735-9c19-c057bb2c6a5e
Crouch, D.J.
f41dfdde-862f-4263-bc99-2b2cfd8bd35e
Duffy, W.
1d7dbfd0-fadf-4232-8ae8-1da1475edbe0
Heeney, M.
50a620f3-51c5-4d5f-9e53-9bbf06636a5f
McCulloch, I.
7bf7b885-809e-4371-8afa-0a3de08a9b5e
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horton, P.N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Pang, H., Skabara, P.J., Crouch, D.J., Duffy, W., Heeney, M., McCulloch, I., Coles, S.J., Horton, P.N. and Hursthouse, M.B. (2007) Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains. Macromolecules, 40 (18), 6585-6593. (doi:10.1021/ma071242n).

Record type: Article

Abstract

A series of conjugated triaryl compounds have been synthesized, consisting of thiophene or selenophene peripheral units and a central 1,3,4-thiadiazole (TDA) heterocycle. X-ray crystallographic studies on four of the materials reveal that the molecules are planar in the solid state and feature an array of intramolecular (heteroatomic) and intermolecular (heteroatomic and -) noncovalent close contacts. Electrochemical oxidative polymerization affords insoluble polymers for EDOT-TDA-EDOT and EDTT-TDA-EDTT. The band gaps of the polymers have been deduced by cyclic voltammetry and electronic absorption spectroscopy and were found to be 1.8-1.9 eV. Both polymers show good stability toward n-doping and the EDTT analogue is more readily reduced than the EDOT-containing system. The enhanced stability toward n-doping, compared with the homopolymers PEDTT and PEDOT, is attributed to the presence of the electron deficient thiadiazole unit. The LUMO of poly(EDTT-TDA-EDTT) is 0.3 eV lower than that of poly(EDOT-TDA-EDOT), demonstrating that the substituent effect of the chalcogen atom is an important contributor to the electronic properties of the polymers.

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Published date: 2007
Keywords: thiophene, optical-properties, intramolecular charge-transfer, substituted polythiophenes, pi-conjugated, polymers, donor, narrow-bandgap, field-effect transistors, oligomers, copolymers

Identifiers

Local EPrints ID: 54353
URI: http://eprints.soton.ac.uk/id/eprint/54353
PURE UUID: 6bbbbc66-7b80-40d5-8388-3483a70ba71b
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for P.N. Horton: ORCID iD orcid.org/0000-0001-8886-2016

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Date deposited: 31 Jul 2008
Last modified: 16 Mar 2024 03:12

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Contributors

Author: H. Pang
Author: P.J. Skabara
Author: D.J. Crouch
Author: W. Duffy
Author: M. Heeney
Author: I. McCulloch
Author: S.J. Coles ORCID iD
Author: P.N. Horton ORCID iD
Author: M.B. Hursthouse

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