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Scientific article
English

Bis(tetrathiafulvalenes) with aromatic bridges: electron delocalization in the oxidized species through EPR and theoretical studies

Contributors

Riobé, François; Avarvari, Narcis; Grosshans, Philippe; Sidorenkova, Helena; Berclaz, Théo; Geoffroy, Michel

Published in

PCCP. Physical chemistry chemical physics, vol. 12, p. 9650-9660

Publication date

2010

Abstract

A series of bis(TTF) donors containing aromatic linkers between the two TTF units has been synthesized in order to investigate on the electronic structure of the oxidized species from an experimental and theoretical point of view. A mono(TTF)-pyridine compound has been also prepared and characterized by single-crystal X-ray diffraction analysis. Oxidation of a solution of 2,6-bis(TTF)-pyridine (TTF-Pyr-TTF) or of 1,3-bis(TTF)-benzene (TTF-Bz-TTF) in CH2Cl2 with less than 0.1 equivalent of [Cp2Fe][PF6] gives rise to a seven-line EPR spectrum consistent with the hyperfine structure calculated by DFT for the corresponding radical monocation. Increasing the proportion of oxidant leads to a four-line hyperfine structure, similar to the quartet pattern observed after oxidation of mono(TTF)-pyridine (Pyr-TTF) or mono(TTF)-benzene (Bz-TTF). In good accordance with the very weak value of J calculated by DFT for the dicationic biradicals these four-line spectra are attributed to [2,6-bis(TTF)-pyridine]2+ and [1,3-bis(TTF)-benzene]2+. Similar experimental results are obtained for 1,4-bis(TTF)-benzene. In this case, however, electrochemical oxidation leads to the monoradical at low potential and to the diradical at higher potential, while only the diradical could be observed by electrochemical oxidation of 2,6-bis(TTF)-pyridine or of 1,3-bis(TTF)-benzene.

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Citation (ISO format)

RIOBÉ, François et al. Bis(tetrathiafulvalenes) with aromatic bridges: electron delocalization in the oxidized species through EPR and theoretical studies. In: PCCP. Physical chemistry chemical physics, 2010, vol. 12, p. 9650–9660. doi: 10.1039/C001014F

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Additional URL for this publication

http://pubs.rsc.org/en/Content/ArticlePDF/2010/CP/C001014F/2010-06-08

Journal ISSN

1463-9076
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Technical informations

Creation

18/03/2011 14:08:04

First validation

18/03/2011 14:08:04

Update

14/03/2023 16:14:23

Status update

14/03/2023 16:14:23

Last indexation

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