title: pi conjugation across the tetrathiafulvalene core: synthesis of extended tetrathiafulvalene derivatives and theoretical analysis of their unusual electrochemical properties
abstract: A series of extended tetrathiafulvalene (TTF) derivatives bearing one or two 1,4-dithiafulven-6-yl substitutents has been prepared. The new compounds present remarkable electrochemical singularities compared with other TTF derivatives, which are strongly affected by the nature of the substitution on the lateral heterocycle(s). This unusual electrochemical behaviour follows a square-scheme sequence and is attributed to structural changes upon oxidation of the pi-donating molecules. Digital simulations of the electrochemical data have been used to reach the values of the kinetic and thermodynamic constants involved in the square scheme. Theoretical calculations establish an important contribution of a highly delocalised resonant form involving a tetravalent sulphur in oxidised species, which could justify the occurrence of an electrochemical behaviour distinct from that of TTF. Finally, third-order susceptibilities chi 3 of two of these systems, for which electron-donating and electron-withdrawing substituents coexist and are conjugated through the TTF pi system, are given.
authors.affiliation: Laboratoire d'Ingenierie Moleculaire et Materiaux Organiques, UMR CNRS 6501, Universite d'Angers, France.
authors.initials: N
authors.lastname: Terkia-Derdra
authors.initials: R
authors.lastname: Andreu
authors.initials: M
authors.lastname: Salle
authors.initials: E
authors.lastname: Levillain
authors.initials: J
authors.lastname: Orduna
authors.initials: J
authors.lastname: Garin
authors.initials: E
authors.lastname: Orti
authors.initials: R
authors.lastname: Viruela
authors.initials: R
authors.lastname: Pou-Amerigo
authors.initials: B
authors.lastname: Sahraoui
authors.initials: A
authors.lastname: Gorgues
authors.initials: JF
authors.lastname: Favard
authors.initials: A
authors.lastname: Riou