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

A new series of ?-extended tetrathiafulvalene derivatives incorporating fused furanodithiino and thienodithiino units: a joint experimental and theoretical study
A new series of ?-extended tetrathiafulvalene derivatives incorporating fused furanodithiino and thienodithiino units: a joint experimental and theoretical study
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.
charge-transfer salts, crystal-structures, bedt-ttf, supramolecular chemistry, molecular-structure, building-blocks, spin-ladder, thiophene, polythiophene, complexation
2822-2830
Berridge, Rory
6aa42596-b293-4914-a1eb-2a974e7f2ed4
Serebryakov, Igor M.
c30b6353-c909-4c7d-8bde-3260a163b8dc
Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Orti, Enrique
ac88b710-db26-4ff8-8bcf-ba52584dd5ee
Viruela, Rafael
4cece555-54ad-41f7-a6ea-bf626c6b616f
Pou-Amérigo, Rosendo
2de3b9df-646c-42b1-aa4f-4e0a3e480252
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Berridge, Rory
6aa42596-b293-4914-a1eb-2a974e7f2ed4
Serebryakov, Igor M.
c30b6353-c909-4c7d-8bde-3260a163b8dc
Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Orti, Enrique
ac88b710-db26-4ff8-8bcf-ba52584dd5ee
Viruela, Rafael
4cece555-54ad-41f7-a6ea-bf626c6b616f
Pou-Amérigo, Rosendo
2de3b9df-646c-42b1-aa4f-4e0a3e480252
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Berridge, Rory, Serebryakov, Igor M., Skabara, Peter J., Orti, Enrique, Viruela, Rafael, Pou-Amérigo, Rosendo, Coles, Simon J. and Hursthouse, Michael B. (2004) A new series of ?-extended tetrathiafulvalene derivatives incorporating fused furanodithiino and thienodithiino units: a joint experimental and theoretical study. Journal of Materials Chemistry, 14 (18), 2822-2830. (doi:10.1039/b404545a).

Record type: Article

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.

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More information

Published date: 2004
Keywords: charge-transfer salts, crystal-structures, bedt-ttf, supramolecular chemistry, molecular-structure, building-blocks, spin-ladder, thiophene, polythiophene, complexation

Identifiers

Local EPrints ID: 20133
URI: https://eprints.soton.ac.uk/id/eprint/20133
PURE UUID: e9481a52-6a6e-4b5a-b04a-39124d95c539
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 23 Feb 2006
Last modified: 06 Jun 2018 12:54

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