| Abstract: | Abstract New dinuclear asymmetric complexes of ruthenium and rhenium, of formula (bpy)(CO)3 ReI(4,4′-bpy)RuII/III(NH3)5]3+/4+ have been prepared and characterized by spectroscopic and electrochemical techniques. In the mixed-valent species ReI, RuIII], the back electron transfer reaction RuII → ReII, that occurs after light excitation, is predicted to be in the Marcus inverted region. This fact is consistent with the observed quenching of the luminiscence of the Re chromophore in (bpy)(CO)3ReI(4,4′-bpy)RuIII(NH3)5]4+, when compared to the parent complex (bpy)(CO)3ReI(4,4′-bpy)]+. A theoretical treatment due to Creutz, Newton and Sutin has been successfully applied to predict the electronic coupling element in the mixed-valent complex. |
