Abstract
The electrochemical behaviour of the binuclear complex NC-Run(bpy)2-CNRuσ(bpy)2-CN+(1) and of the trinuclear complexes NC-Ruσ(bpy)2-CN-Ruσ(bpy)2-NC-Ruσ(bpy)2CN2+ (2), NC-Ruσ(bpy)2-CN-Ruσ(DCE-bpy)2-NC-Ruσ(bpy)2-CNP2+ (3) is described. These complexes give rise to extended redox series. Metal localized one-electron oxidation processes are assigned on the basis of the comparison with the model Ru(bpy)2(CN)2 complex. Ligand localized reductions are fully reversible at -54°C. The assignment of the redox sites, which are involved in such processes, is given taking into account the different electronic perturbation introduced at metal centres by the asymmetric bridging ligand as well as the energy difference between π* accepting orbital of the different polypyridine ligands. The experimentally determined redox series consist of nine, thirteen and fourtheen redox steps for the binuclear complex 1 and for the trinuclear complexes 2 and 3 respectively.
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