Interplay between Organic-Organometallic Electrophores within Bis(cyclopentadienyl)Molybdenum Dithiolene Tetrathiafulvalene Complexes.
Tetrathiafulvalenes (TTF) and bis(cyclopentadienyl) molybdenum dithiolene complexes, Cp2Mo(dithiolene) complexes, are known separately to act as good electron donor molecules. For an investigation of the interaction between both electrophores, two types of complexes were synthesized and characterized. The first type has one Cp2Mo fragment coordinated to one TTF dithiolate ligand, and the second type has one TTF bis(dithiolate) bridging two Cp2Mo fragments. Comparisons of the electrochemical properties of these complexes with those of models of each separate electrophore provide evidence for their mutual influence. All of these complexes act as very good electron donors with a first oxidation potential 430 mV lower than the tetrakis(methylthio)TTF. DFT calculations suggest that the HOMO of the neutral complex and the SOMO of the cation are delocalized across the whole TTF dithiolate ligand. The X-ray crystal structure analyses of the neutral and the mono-oxidized Cp2Mo(dithiolene)(bismethylthio)TTF complexes are consistent with the delocalized assignment of the highest occupied frontier molecular orbitals. UV-vis-NIR spectroelectrochemical investigations confirm this electronic delocalization within the TTF dithiolate ligand.
Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, Bât 10A, 35042 Rennes cedex, France.
Nathalie
N
Bellec
Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, Bât 10A, 35042 Rennes cedex, France.
Antoine
A
Vacher
Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, Bât 10A, 35042 Rennes cedex, France.
Frédéric
F
Barrière
Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, Bât 10A, 35042 Rennes cedex, France.
Zijun
Z
Xu
Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, Bât 10A, 35042 Rennes cedex, France.
Thierry
T
Roisnel
Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, Bât 10A, 35042 Rennes cedex, France.
Dominique
D
Lorcy