A new series of pi-extended tetrathiafulvalene derivatives incorporating fused furanodithiino and thienodithiino units: a joint experimental and theoretical study

R. Berridge, I.M. Serebryakov, P.J. Skabara, E. Ortí, R. Viruela, R. Pou-Amerigo, S.J. Coles, M.B. Hursthouse

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

A new family of tetrathiafulvalenes has been prepared. The materials exhibit complex redox behaviour related to the electronic influence of the 1,4-dithiin moieties embedded within the framework of the molecules. The X-ray crystal structure of compound 4 reveals an unusual non-planar conformation of the heterocyclic compound, with the TTF fragment adopting a boat conformation. Theoretical calculations, performed at the DFT level (B3P86/6-31G*), confirm the boatlike structure (C-2v symmetry) as the most stable conformation for this family of tetrathiafulvalenes. Upon oxidation, electrons are extracted from the whole molecule and the radical cations and dications remain highly distorted from planarity. For the dications, the 1,4-dithiin units present foldings of similar to40degrees suggesting the possibility of reaching higher oxidation states in agreement with experimental results. For the tetracations, both the TTF nucleus and the 1,4-dithiin units are singly-charged and become planar. The tetracations therefore present fully-planar, pi-delocalised structures and are stabilised by the gain of aromaticity of the TTF and 1,4-dithiin electron-donor units.
LanguageEnglish
Pages2822-2830
Number of pages8
JournalJournal of Materials Chemistry
Volume14
Issue number18
DOIs
Publication statusPublished - 2004

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Conformations
Derivatives
Heterocyclic Compounds
Oxidation
Molecules
Electrons
Boats
Discrete Fourier transforms
Cations
Crystal structure
Positive ions
X rays
tetrathiafulvalene
Oxidation-Reduction

Keywords

  • charge-transfer salts
  • crystal-structurs
  • bedt-ttf
  • supramolecular chemistry
  • molecular-structure
  • buidling-blocks
  • spin-ladder
  • thiophene
  • polythiophene
  • complexation

Cite this

Berridge, R. ; Serebryakov, I.M. ; Skabara, P.J. ; Ortí, E. ; Viruela, R. ; Pou-Amerigo, R. ; Coles, S.J. ; Hursthouse, M.B. / A new series of pi-extended tetrathiafulvalene derivatives incorporating fused furanodithiino and thienodithiino units: a joint experimental and theoretical study. In: Journal of Materials Chemistry. 2004 ; Vol. 14, No. 18. pp. 2822-2830.
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Berridge, R, Serebryakov, IM, Skabara, PJ, Ortí, E, Viruela, R, Pou-Amerigo, R, Coles, SJ & Hursthouse, MB 2004, 'A new series of pi-extended tetrathiafulvalene derivatives incorporating fused furanodithiino and thienodithiino units: a joint experimental and theoretical study' Journal of Materials Chemistry, vol. 14, no. 18, pp. 2822-2830. https://doi.org/10.1039/b404545a

A new series of pi-extended tetrathiafulvalene derivatives incorporating fused furanodithiino and thienodithiino units: a joint experimental and theoretical study. / Berridge, R.; Serebryakov, I.M.; Skabara, P.J.; Ortí, E.; Viruela, R.; Pou-Amerigo, R.; Coles, S.J.; Hursthouse, M.B.

In: Journal of Materials Chemistry, Vol. 14, No. 18, 2004, p. 2822-2830.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A new series of pi-extended tetrathiafulvalene derivatives incorporating fused furanodithiino and thienodithiino units: a joint experimental and theoretical study

AU - Berridge, R.

AU - Serebryakov, I.M.

AU - Skabara, P.J.

AU - Ortí, E.

AU - Viruela, R.

AU - Pou-Amerigo, R.

AU - Coles, S.J.

AU - Hursthouse, M.B.

PY - 2004

Y1 - 2004

N2 - A new family of tetrathiafulvalenes has been prepared. The materials exhibit complex redox behaviour related to the electronic influence of the 1,4-dithiin moieties embedded within the framework of the molecules. The X-ray crystal structure of compound 4 reveals an unusual non-planar conformation of the heterocyclic compound, with the TTF fragment adopting a boat conformation. Theoretical calculations, performed at the DFT level (B3P86/6-31G*), confirm the boatlike structure (C-2v symmetry) as the most stable conformation for this family of tetrathiafulvalenes. Upon oxidation, electrons are extracted from the whole molecule and the radical cations and dications remain highly distorted from planarity. For the dications, the 1,4-dithiin units present foldings of similar to40degrees suggesting the possibility of reaching higher oxidation states in agreement with experimental results. For the tetracations, both the TTF nucleus and the 1,4-dithiin units are singly-charged and become planar. The tetracations therefore present fully-planar, pi-delocalised structures and are stabilised by the gain of aromaticity of the TTF and 1,4-dithiin electron-donor units.

AB - A new family of tetrathiafulvalenes has been prepared. The materials exhibit complex redox behaviour related to the electronic influence of the 1,4-dithiin moieties embedded within the framework of the molecules. The X-ray crystal structure of compound 4 reveals an unusual non-planar conformation of the heterocyclic compound, with the TTF fragment adopting a boat conformation. Theoretical calculations, performed at the DFT level (B3P86/6-31G*), confirm the boatlike structure (C-2v symmetry) as the most stable conformation for this family of tetrathiafulvalenes. Upon oxidation, electrons are extracted from the whole molecule and the radical cations and dications remain highly distorted from planarity. For the dications, the 1,4-dithiin units present foldings of similar to40degrees suggesting the possibility of reaching higher oxidation states in agreement with experimental results. For the tetracations, both the TTF nucleus and the 1,4-dithiin units are singly-charged and become planar. The tetracations therefore present fully-planar, pi-delocalised structures and are stabilised by the gain of aromaticity of the TTF and 1,4-dithiin electron-donor units.

KW - charge-transfer salts

KW - crystal-structurs

KW - bedt-ttf

KW - supramolecular chemistry

KW - molecular-structure

KW - buidling-blocks

KW - spin-ladder

KW - thiophene

KW - polythiophene

KW - complexation

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UR - http://dx.doi.org/10.1039/b404545a

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DO - 10.1039/b404545a

M3 - Article

VL - 14

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EP - 2830

JO - Journal of Materials Chemistry

T2 - Journal of Materials Chemistry

JF - Journal of Materials Chemistry

SN - 0959-9428

IS - 18

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