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The first direct experimental comparison between the hugely contrasting properties of PEDOT and the all-sulfur analogue PEDOT by analogy with well-defined EDTT-EDOT copolymers

The first direct experimental comparison between the hugely contrasting properties of PEDOT and the all-sulfur analogue PEDOT by analogy with well-defined EDTT-EDOT copolymers
The first direct experimental comparison between the hugely contrasting properties of PEDOT and the all-sulfur analogue PEDOT by analogy with well-defined EDTT-EDOT copolymers
The structures of poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedithiathiophene) (PEDTT) vary only in the substituent chalcogen atoms, yet the electronic properties of the materials are surprisingly dissimilar. The difference in electronic band gaps is approximately 0.8 eV and the polymers behave very differently upon p-doping. Two new terthiophenes have been synthesised using Negishi coupling methods. The X-ray crystal structures of EDOT-EDTT-EDOT (OSO) and EDTT-EDOT-EDTT (SOS) show strong intramolecular chalcogen-chalcogen contacts which are responsible for persistent conformers in solution and solid state, although significant interchain interactions should also influence the properties of the materials. SOS and OSO can be polymerised by electrochemical oxidation to give the corresponding, well-defined poly(terthiophenes) PSOS and POSO. Spectroelectrochemical studies on all four polymers reveal strong similarities between PEDTT and PSOS, and between PEDOT and POSO. Together with independent electrochemical and absorption studies, the results indicate that the unique properties of PEDOT are influenced more by conformational effects (intrachain S center dot center dot center dot O contacts) than substituent effects.
low-band-gap, photoelectron-spectroscopy, intrinsic conductivity, polymers, derivatives, poly(3, 4-ethylenedioxythiophene), electropolymerization, thiophene, 3, 4-ethylenedioxythiophene, tetrathiafulvalene
4783-4792
Spencer, Howard J.
e712937c-ff3d-462a-80f8-7d4748531999
Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Giles, Mark
69c73c59-9823-45d9-bd5c-6137eac4616a
McCulloch, Iain
7cac4a7c-75ab-47da-85b7-0ae78f600ee0
Coles, Simon J.
65bb28e4-4917-43f5-a770-a00017d6783f
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28
Spencer, Howard J.
e712937c-ff3d-462a-80f8-7d4748531999
Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Giles, Mark
69c73c59-9823-45d9-bd5c-6137eac4616a
McCulloch, Iain
7cac4a7c-75ab-47da-85b7-0ae78f600ee0
Coles, Simon J.
65bb28e4-4917-43f5-a770-a00017d6783f
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28

Spencer, Howard J., Skabara, Peter J., Giles, Mark, McCulloch, Iain, Coles, Simon J. and Hursthouse, Michael B. (2005) The first direct experimental comparison between the hugely contrasting properties of PEDOT and the all-sulfur analogue PEDOT by analogy with well-defined EDTT-EDOT copolymers. Journal of Materials Chemistry, 15 (45), 4783-4792. (doi:10.1039/b511075k).

Record type: Article

Abstract

The structures of poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedithiathiophene) (PEDTT) vary only in the substituent chalcogen atoms, yet the electronic properties of the materials are surprisingly dissimilar. The difference in electronic band gaps is approximately 0.8 eV and the polymers behave very differently upon p-doping. Two new terthiophenes have been synthesised using Negishi coupling methods. The X-ray crystal structures of EDOT-EDTT-EDOT (OSO) and EDTT-EDOT-EDTT (SOS) show strong intramolecular chalcogen-chalcogen contacts which are responsible for persistent conformers in solution and solid state, although significant interchain interactions should also influence the properties of the materials. SOS and OSO can be polymerised by electrochemical oxidation to give the corresponding, well-defined poly(terthiophenes) PSOS and POSO. Spectroelectrochemical studies on all four polymers reveal strong similarities between PEDTT and PSOS, and between PEDOT and POSO. Together with independent electrochemical and absorption studies, the results indicate that the unique properties of PEDOT are influenced more by conformational effects (intrachain S center dot center dot center dot O contacts) than substituent effects.

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More information

Published date: 7 December 2005
Keywords: low-band-gap, photoelectron-spectroscopy, intrinsic conductivity, polymers, derivatives, poly(3, 4-ethylenedioxythiophene), electropolymerization, thiophene, 3, 4-ethylenedioxythiophene, tetrathiafulvalene

Identifiers

Local EPrints ID: 20913
URI: http://eprints.soton.ac.uk/id/eprint/20913
PURE UUID: ff0418dc-a8d0-44b2-b830-b75c0fb3cbb5

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Date deposited: 01 Mar 2006
Last modified: 15 Jul 2019 19:25

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Contributors

Author: Howard J. Spencer
Author: Peter J. Skabara
Author: Mark Giles
Author: Iain McCulloch
Author: Simon J. Coles
Author: Michael B. Hursthouse

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