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

Hao Pang, Peter Skabara, David J. Crouch, Warren Duffy, Martin Heeney, Iain McCulloch, Simon J. Coles, Peter N. Horton, Michael B. Hursthouse

Research output: Contribution to journalArticle

42 Citations (Scopus)

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 π−π) 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.
LanguageUndefined/Unknown
Pages6585-6593
Number of pages9
JournalMacromolecules
Volume40
Issue number18
DOIs
Publication statusPublished - 4 Sep 2007

Keywords

  • polymers
  • thiadiazole units
  • triaryl compounds
  • polythiophene chains

Cite this

Pang, H., Skabara, P., Crouch, D. J., Duffy, W., Heeney, M., McCulloch, I., ... Hursthouse, M. B. (2007). Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains. Macromolecules, 40(18), 6585-6593. https://doi.org/10.1021/ma071242n
Pang, Hao ; Skabara, Peter ; Crouch, David J. ; Duffy, Warren ; Heeney, Martin ; McCulloch, Iain ; Coles, Simon J. ; Horton, Peter N. ; Hursthouse, Michael B. / Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains. In: Macromolecules. 2007 ; Vol. 40, No. 18. pp. 6585-6593.
@article{72321732932f48a9b8271c8d4245c93b,
title = "Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains",
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 π−π) 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.",
keywords = "polymers, thiadiazole units , triaryl compounds , polythiophene chains",
author = "Hao Pang and Peter Skabara and Crouch, {David J.} and Warren Duffy and Martin Heeney and Iain McCulloch and Coles, {Simon J.} and Horton, {Peter N.} and Hursthouse, {Michael B.}",
year = "2007",
month = "9",
day = "4",
doi = "10.1021/ma071242n",
language = "Undefined/Unknown",
volume = "40",
pages = "6585--6593",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "18",

}

Pang, H, Skabara, P, Crouch, DJ, Duffy, W, Heeney, M, McCulloch, I, Coles, SJ, Horton, PN & Hursthouse, MB 2007, 'Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains' Macromolecules, vol. 40, no. 18, pp. 6585-6593. https://doi.org/10.1021/ma071242n

Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains. / Pang, Hao; Skabara, Peter; Crouch, David J.; Duffy, Warren; Heeney, Martin; McCulloch, Iain; Coles, Simon J.; Horton, Peter N.; Hursthouse, Michael B.

In: Macromolecules, Vol. 40, No. 18, 04.09.2007, p. 6585-6593.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains

AU - Pang, Hao

AU - Skabara, Peter

AU - Crouch, David J.

AU - Duffy, Warren

AU - Heeney, Martin

AU - McCulloch, Iain

AU - Coles, Simon J.

AU - Horton, Peter N.

AU - Hursthouse, Michael B.

PY - 2007/9/4

Y1 - 2007/9/4

N2 - 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 π−π) 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.

AB - 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 π−π) 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.

KW - polymers

KW - thiadiazole units

KW - triaryl compounds

KW - polythiophene chains

U2 - 10.1021/ma071242n

DO - 10.1021/ma071242n

M3 - Article

VL - 40

SP - 6585

EP - 6593

JO - Macromolecules

T2 - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 18

ER -

Pang H, Skabara P, Crouch DJ, Duffy W, Heeney M, McCulloch I et al. Structural and electronic effects of 1,3,4-thiadiazole units incorporated into polythiophene chains. Macromolecules. 2007 Sep 4;40(18):6585-6593. https://doi.org/10.1021/ma071242n