title: Electroactive ligands: the first metal complexes of tetrathiafulvenyl-acetylacetonate.
abstract: The reaction of tris(alkylthio)tetrathiafulvalene thiolates with 3-chloro-2,4-pentanedione affords tetrathiafulvalene (TTF) moieties substituted by the acetylacetone function (TTFSacacH), precursors of novel redox-active ligands: the acetylacetonate ions (TTFSacac). These TTFSacacHs have been characterized by X-ray diffraction analyses, and similar trends have been observed, such as a TTF core almost planar and the acetylacetone substituent located in a plane almost perpendicular to the plane formed by the TTF core. Their chelating ability has been demonstrated by the formation of the corresponding M(TTFSacac)2(pyridine)2 complexes in the presence of M(II)(OAc)2.H2O (M = Ni2+, Zn2+). These complexes with TTFSacac moieties, Ni(TTFSacac)2(pyridine)2, 6b, and Zn(TTFSacac)2(pyridine)2, 7b, have been characterized by X-ray diffraction analyses, showing in all structures the metal(II) center chelated by two TTFacac units in the equatorial plane and the octahedral coordination geometry around the metal completed by two axial pyridine ligands. Cyclic voltammetry and UV-visible-near infrared spectroscopic measurements have evidenced a sizable interaction between the two electroactive ligands and the stabilization of a mixed-valence state in the one-electron oxidized complexes.
authors.affiliation: Groupe Hétérochimie et Matériaux Electroactifs, SESO UMR 6510 CNRS--Université de Rennes 1, Institut de Chimie de Rennes, 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: Stéphanie
authors.initials: S
authors.lastname: Chopin
authors.forename: Eric
authors.initials: E
authors.lastname: Levillain
authors.forename: Thierry
authors.initials: T
authors.lastname: Roisnel
authors.forename: Rodolphe
authors.initials: R
authors.lastname: Clérac
authors.forename: Dominique
authors.initials: D
authors.lastname: Lorcy