UNIGE document Scientific Article
previous document  unige:14784  next document
add to browser collection
Title

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

Authors
Riobé, François
Avarvari, Narcis
Sidorenkova, Helena
Published in Physical Chemistry Chemical Physics. 2010, vol. 12, p. 9650-9660
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.
Stable URL http://archive-ouverte.unige.ch/unige:14784
Full text
Identifiers
Structures

131 hits

30 downloads

Update

Deposited on : 2011-03-18

Export document
Format :
Citation style :