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Synthesis and electropolymerisation of 3',4'-bis(alkylsulfanyl)terthiophenes and the significance of the fused dithiin ring in 2,5-dithienyl-3,4-ethylenedithiothiophene (DT-EDTT)

Synthesis and electropolymerisation of 3',4'-bis(alkylsulfanyl)terthiophenes and the significance of the fused dithiin ring in 2,5-dithienyl-3,4-ethylenedithiothiophene (DT-EDTT)
Synthesis and electropolymerisation of 3',4'-bis(alkylsulfanyl)terthiophenes and the significance of the fused dithiin ring in 2,5-dithienyl-3,4-ethylenedithiothiophene (DT-EDTT)
A new series of regioregular poly(terthiophenes), bearing bis(thioether) side groups, has been prepared by electrochemical oxidation. Cyclic voltammetry of the parent trimers reveals an increase in electron donating ability in cyclic thioether derivatives. For example, one compound containing a central ethylenedithiothiophene (EDTT) unit gives two irreversible oxidation peaks which are significantly lower than the corresponding values for the structurally analogous bis(methylthio) derivative (?E(1ox) = 170 mV, ?E(2ox) = 30 mV). The difference in oxidation potentials of each terthiophene in acetonitrile solution can be explained by examining the highest occupied molecular orbital (HOMO) energies. The electrochemical behaviour of the polymers illustrates the increase in p-doping ability of the EDTT-containing polymer. The cyclic voltammograms and electronic absorption spectra of the polymers show that the polymers containing cyclic thioether units have the lowest bandgap in the series (ca. 1.4 V and 1.5 eV, respectively). Photoinduced IR spectroscopy of poly(dithienyl-3,4-ethylenedithiothiophene) provides evidence of a long-living photoexcited charged state in the polymer.
x-ray structure, conducting polymers, conjugated polymers, crystal-structures, electrochemical synthesis, infrared activity, poly(3, 4-ethylenedioxythiophene), oligothiophenes, 3, 4-ethylenedioxythiophene, poly(thiophenes)
500-510
Pozo-Gonzalo, Cristina
b478e502-07a4-44f4-8a32-e9c6b98f7206
Khan, Tahir
62b62b1c-8266-451d-bcbe-9c4aa09c3440
McDouall, Joseph J.W.
4ca54dfa-6b19-41d4-b531-a5cf701fdd68
Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Roberts, Donna M.
1c5733a2-6d64-4577-9144-d0e5edb753b9
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Neugebauer, Helmut
0717ac95-7b07-46b7-bfc0-32b611868953
Cravino, Antonio
5f509d3b-1b17-416f-bf03-902cb2994fdf
Sariciftci, N. Serdar
c911b1f5-476d-41fe-aa60-e682cf3e770e
Pozo-Gonzalo, Cristina
b478e502-07a4-44f4-8a32-e9c6b98f7206
Khan, Tahir
62b62b1c-8266-451d-bcbe-9c4aa09c3440
McDouall, Joseph J.W.
4ca54dfa-6b19-41d4-b531-a5cf701fdd68
Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Roberts, Donna M.
1c5733a2-6d64-4577-9144-d0e5edb753b9
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Neugebauer, Helmut
0717ac95-7b07-46b7-bfc0-32b611868953
Cravino, Antonio
5f509d3b-1b17-416f-bf03-902cb2994fdf
Sariciftci, N. Serdar
c911b1f5-476d-41fe-aa60-e682cf3e770e

Pozo-Gonzalo, Cristina, Khan, Tahir, McDouall, Joseph J.W., Skabara, Peter J., Roberts, Donna M., Light, Mark E., Coles, Simon J., Hursthouse, Michael B., Neugebauer, Helmut, Cravino, Antonio and Sariciftci, N. Serdar (2002) Synthesis and electropolymerisation of 3',4'-bis(alkylsulfanyl)terthiophenes and the significance of the fused dithiin ring in 2,5-dithienyl-3,4-ethylenedithiothiophene (DT-EDTT). Journal of Materials Chemistry, 12 (3), 500-510. (doi:10.1039/b109017h).

Record type: Article

Abstract

A new series of regioregular poly(terthiophenes), bearing bis(thioether) side groups, has been prepared by electrochemical oxidation. Cyclic voltammetry of the parent trimers reveals an increase in electron donating ability in cyclic thioether derivatives. For example, one compound containing a central ethylenedithiothiophene (EDTT) unit gives two irreversible oxidation peaks which are significantly lower than the corresponding values for the structurally analogous bis(methylthio) derivative (?E(1ox) = 170 mV, ?E(2ox) = 30 mV). The difference in oxidation potentials of each terthiophene in acetonitrile solution can be explained by examining the highest occupied molecular orbital (HOMO) energies. The electrochemical behaviour of the polymers illustrates the increase in p-doping ability of the EDTT-containing polymer. The cyclic voltammograms and electronic absorption spectra of the polymers show that the polymers containing cyclic thioether units have the lowest bandgap in the series (ca. 1.4 V and 1.5 eV, respectively). Photoinduced IR spectroscopy of poly(dithienyl-3,4-ethylenedithiothiophene) provides evidence of a long-living photoexcited charged state in the polymer.

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More information

Published date: 2002
Keywords: x-ray structure, conducting polymers, conjugated polymers, crystal-structures, electrochemical synthesis, infrared activity, poly(3, 4-ethylenedioxythiophene), oligothiophenes, 3, 4-ethylenedioxythiophene, poly(thiophenes)

Identifiers

Local EPrints ID: 19839
URI: http://eprints.soton.ac.uk/id/eprint/19839
PURE UUID: d2f6f120-2f53-4e54-a2bb-ab3f00b19fca
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 22 Feb 2006
Last modified: 16 Mar 2024 03:05

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Contributors

Author: Cristina Pozo-Gonzalo
Author: Tahir Khan
Author: Joseph J.W. McDouall
Author: Peter J. Skabara
Author: Donna M. Roberts
Author: Mark E. Light ORCID iD
Author: Simon J. Coles ORCID iD
Author: Helmut Neugebauer
Author: Antonio Cravino
Author: N. Serdar Sariciftci

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