title: Crown ether vinylogous tetrathiafulvalene receptors: complexation interference on the molecular movements triggered by electron transfer.
abstract: The synthesis of a series of crown ether substituted vinylogous tetrathiafulvalenes (TTFVs) has been carried out through oxidative coupling of bisdithiafulvenes. These new receptors have been fully characterized using electrochemical, spectroelectrochemical, and molecular modeling experiments. These studies show that, upon oxidation, either a clip movement (TTFVs 3a,b) or a stretch movement (TTFV 3c) occurs, depending on the length of the crown ether chains. Preliminary electrochemical studies, undertaken on TTFV 3c in dichloromethane, show a little shift of the first standard oxidation potential toward more positive values upon addition of the Pb(2+) ion, but a considerable variation of the electron-transfer kinetics. This result introduces an interesting concept for the preparation of sensors not based on thermodynamic variations but on kinetic modifications of the electron transfer.
authors.affiliation: Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, Bât 10A, 35042 Rennes cedex, France.
authors.forename: Julien
authors.initials: J
authors.lastname: Massue
authors.forename: Nathalie
authors.initials: N
authors.lastname: Bellec
authors.forename: Michel
authors.initials: M
authors.lastname: Guerro
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Bergamini
authors.forename: Philippe
authors.initials: P
authors.lastname: Hapiot
authors.forename: Dominique
authors.initials: D
authors.lastname: Lorcy