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

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

Research output: Contribution to journalArticle

84 Citations (Scopus)

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.
LanguageEnglish
Pages4783-4792
Number of pages9
JournalJournal of Materials Chemistry
Volume15
Issue number45
DOIs
Publication statusPublished - 7 Dec 2005

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Chalcogens
Sulfur
Copolymers
Electrochemical oxidation
Polymers
Electronic properties
Contacts (fluid mechanics)
Energy gap
Crystal structure
Doping (additives)
X rays
Atoms
poly(3,4-ethylene dioxythiophene)
alpha-terthienyl

Keywords

  • low-band-gap
  • photoelectron-spectroscopy
  • intrinsic conductivity
  • polymers
  • derivatives
  • poly(3
  • 4-ethylenedioxythiophene)
  • electropolymerization
  • thiophene
  • 3
  • 4-ethylenedioxythiophene
  • tetrathiafulvalene

Cite this

Spencer, Howard J. ; Skabara, Peter J. ; Giles, Mark ; McCulloch, Iain ; Coles, Simon J. ; Hursthouse, Michael B. / 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. In: Journal of Materials Chemistry. 2005 ; Vol. 15, No. 45. pp. 4783-4792.
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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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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. / Spencer, Howard J.; Skabara, Peter J.; Giles, Mark; McCulloch, Iain; Coles, Simon J.; Hursthouse, Michael B.

In: Journal of Materials Chemistry, Vol. 15, No. 45, 07.12.2005, p. 4783-4792.

Research output: Contribution to journalArticle

TY - JOUR

T1 - 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

AU - Spencer, Howard J.

AU - Skabara, Peter J.

AU - Giles, Mark

AU - McCulloch, Iain

AU - Coles, Simon J.

AU - Hursthouse, Michael B.

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N2 - 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.

AB - 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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KW - 4-ethylenedioxythiophene)

KW - electropolymerization

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KW - 3

KW - 4-ethylenedioxythiophene

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DO - 10.1039/b511075k

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EP - 4792

JO - Journal of Materials Chemistry

T2 - Journal of Materials Chemistry

JF - Journal of Materials Chemistry

SN - 0959-9428

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