Stereochemical influences on intervalence charge transfer in homodinuclear complexes of ruthenium

The synthesis of polynuclear transition metal assemblies and their electrochemical, photochemical, and photophysical properties have attracted significant recent interest; this has been motivated largely by the potential of multicomponent systems as a basis of novel applicable materials.1 However, the existence of the stereochemical complexities inherent in such systems, and their influence on intramolecular energy- and electrontransfer processes, has not always been acknowledged^2. Work in our laboratory has established synthetic methodologies for the isolation of the stereoisomers of a variety of mono-, di-, and trinuclear complexes^2,3. Significantly, this work has given rise to the first three examples of differences in the spectral, electrochemical, and photophysical properties of stereoisomers in such assemblies^2,4