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Article Dans Une Revue Journal of the American Chemical Society Année : 1995

Intervalence Transitions in Mixed Valence Bis(tetrathiafulvalene) Compounds

Résumé

The series of new bis(tetrathiafulva1ene) [bis(TTF)] compounds 10-12a,b have been synthetized with the TTF-like synthon 8a,b, previously used to prepare the pyrazine-fused bis("F) 7a,b. These compounds exhibit four reversible sequential one-electron oxidation steps, on the basis of cyclic voltammetry. For the cation radicals 7b.+,10 .+,and 12.+, generated electrochemically, rather intense and broad bands in the near-IR region, specific of class 11 mixed valence compounds, were found. Theoretical calculations at the semiempirical AM1 level as well as at the ab-initio level indicated that these cation radicals are charge-distributions localized as related to mixed valence species. These calculations also allowed the low-energy absorption bands to be assigned to intervalence transitions; these transitions imply the existence of multiple low-lying excited states that are non-adiabatically coupled to the ground-state of these open-shell species.

Dates et versions

hal-01741148 , version 1 (22-03-2018)

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Khalid Lahlil, Alec Moradpour, Christopher Bowlas, Frederic Menou, Patrick Cassoux, et al.. Intervalence Transitions in Mixed Valence Bis(tetrathiafulvalene) Compounds. Journal of the American Chemical Society, 1995, 117 (40), pp.9995 - 10002. ⟨10.1021/ja00145a009⟩. ⟨hal-01741148⟩
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