Linearly extended hybrid tetrathiafulvalene analogues with bridged dithienylethyleneπ-conjugating spacers - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Materials Chemistry Année : 1997

Linearly extended hybrid tetrathiafulvalene analogues with bridged dithienylethyleneπ-conjugating spacers

Soazig Le Moustarder
  • Fonction : Auteur
Philippe Blanchard
Bertrand Illien
  • Fonction : Auteur
Amédée Riou
  • Fonction : Auteur
Jesus Orduna
  • Fonction : Auteur
Javier Garin
  • Fonction : Auteur
Jean Roncali
  • Fonction : Auteur

Résumé

New linearly extended π-electron donors based on bridged dithienylethylene (DTE) end-capped with diversely substituted 1,3-dithiol-2-ylidene electron-releasing groups have been synthesized by Wittig–Horner olefination of appropriate aldehydes. Cyclic voltammetry shows that whereas the unbridged analogues are directly oxidized to the dication state through a two-electron transfer, rigidification of the DTE spacer leads to the splitting of the two-electron wave into two successive one-electron steps due to the decrease of the potential corresponding to the formation of the cation radical. This unusual electrochemical behaviour is interpreted with the help of theoretical calculations which suggest that these effects are related to the enhanced electron delocalization resulting from the rigidification of the DTE spacer. This conclusion is supported by an X-ray diffraction structural analysis which reveals that in addition to a fully planar conformation stabilized by intramolecular S‥S interactions, the bridging of the DTE spacer leads to a significant reduction of bond length alternation.

Domaines

Chimie

Dates et versions

hal-03409172 , version 1 (29-10-2021)

Identifiants

Citer

Hugues Brisset, Soazig Le Moustarder, Philippe Blanchard, Bertrand Illien, Amédée Riou, et al.. Linearly extended hybrid tetrathiafulvalene analogues with bridged dithienylethyleneπ-conjugating spacers. Journal of Materials Chemistry, 1997, 7 (10), pp.2027-2032. ⟨10.1039/A701463E⟩. ⟨hal-03409172⟩

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