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)

Cristina Pozo-Gonzalo, Tahir Khan, Joseph J.W. McDouall, Peter J. Skabara, Donna M. Roberts, Mark E. Light, Simon J. Coles, Michael B. Hursthouse, Helmut Neugebauer, Antonio Cravino, N. Serdar Sariciftci

Research output: Contribution to journalArticle

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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 (DeltaE(1ox) = 170 mV, DeltaE(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.
LanguageEnglish
Pages500-510
Number of pages10
JournalJournal of Materials Chemistry
Volume12
Issue number3
DOIs
Publication statusPublished - 2002

Fingerprint

Electropolymerization
Polymers
Sulfides
Bearings (structural)
Derivatives
Oxidation
Electrochemical oxidation
Molecular orbitals
Acetonitrile
Cyclic voltammetry
Absorption spectra
Infrared spectroscopy
Energy gap
Doping (additives)
alpha-terthienyl
Electrons

Keywords

  • x-ray structure
  • conducting polymers
  • conjugated polymers
  • crystal-strucutres
  • electrochemical synthesis
  • infrared activity
  • poly(3
  • 4-ethylenedioxythiophene)
  • oligothiophenes
  • 3
  • 4-ethylenedioxythiophene
  • poly(thiophenes)

Cite this

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 ; Sariciftci, N. Serdar. / 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). In: Journal of Materials Chemistry. 2002 ; Vol. 12, No. 3. pp. 500-510.
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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 (DeltaE(1ox) = 170 mV, DeltaE(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.",
keywords = "x-ray structure, conducting polymers, conjugated polymers, crystal-strucutres, electrochemical synthesis, infrared activity, poly(3, 4-ethylenedioxythiophene), oligothiophenes, 3, 4-ethylenedioxythiophene, poly(thiophenes)",
author = "Cristina Pozo-Gonzalo and Tahir Khan and McDouall, {Joseph J.W.} and Skabara, {Peter J.} and Roberts, {Donna M.} and Light, {Mark E.} and Coles, {Simon J.} and Hursthouse, {Michael B.} and Helmut Neugebauer and Antonio Cravino and Sariciftci, {N. Serdar}",
year = "2002",
doi = "10.1039/b109017h",
language = "English",
volume = "12",
pages = "500--510",
journal = "Journal of Materials Chemistry",
issn = "0959-9428",
number = "3",

}

Pozo-Gonzalo, C, Khan, T, McDouall, JJW, Skabara, PJ, Roberts, DM, Light, ME, Coles, SJ, Hursthouse, MB, Neugebauer, H, Cravino, A & Sariciftci, NS 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, vol. 12, no. 3, pp. 500-510. https://doi.org/10.1039/b109017h

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). / 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; Sariciftci, N. Serdar.

In: Journal of Materials Chemistry, Vol. 12, No. 3, 2002, p. 500-510.

Research output: Contribution to journalArticle

TY - JOUR

T1 - 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)

AU - Pozo-Gonzalo, Cristina

AU - Khan, Tahir

AU - McDouall, Joseph J.W.

AU - Skabara, Peter J.

AU - Roberts, Donna M.

AU - Light, Mark E.

AU - Coles, Simon J.

AU - Hursthouse, Michael B.

AU - Neugebauer, Helmut

AU - Cravino, Antonio

AU - Sariciftci, N. Serdar

PY - 2002

Y1 - 2002

N2 - 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 (DeltaE(1ox) = 170 mV, DeltaE(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.

AB - 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 (DeltaE(1ox) = 170 mV, DeltaE(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.

KW - x-ray structure

KW - conducting polymers

KW - conjugated polymers

KW - crystal-strucutres

KW - electrochemical synthesis

KW - infrared activity

KW - poly(3

KW - 4-ethylenedioxythiophene)

KW - oligothiophenes

KW - 3

KW - 4-ethylenedioxythiophene

KW - poly(thiophenes)

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UR - http://dx.doi.org/10.1039/b109017h

U2 - 10.1039/b109017h

DO - 10.1039/b109017h

M3 - Article

VL - 12

SP - 500

EP - 510

JO - Journal of Materials Chemistry

T2 - Journal of Materials Chemistry

JF - Journal of Materials Chemistry

SN - 0959-9428

IS - 3

ER -