Abstract
ABSTRACTRod-shaped dinuclear Ru/Os complexes, [Os(bimpy-X)(BL)M(bimpyH2)]n+( M = Os or Ru; bimpyH2 = 2,6-bis(benzimidazol-2-yl)pyridine, X = anchoring group such as disulfide and phosphonic acid, BL =bis tridentate ligand), as a potential candidate for molecular devices have been successfully self-assembled on gold or indium-tin oxide (ITO) electrode by using anchoring ligands. The Ru/Os assembled complexes on the solid surface were well characterized by means of MALDI-TOF mass spectrometry, XPS, and electrochemical measurements. Novel proton-coupled electron transfer reaction of the self-assembled dinuclear complex on M(bimpyH2) moiety (M = Ru or Os) was confirmed by analyzing the plots of oxidation potential, E1/2, vs pH. In the case of M = Os and BL = 1,4-bis(terpyridyl)benzene (btpb), two stepwise one-electron oxidation waves were observed at 0.67 V for the Os(III/II) process and 0.88 V vs Ag/AgCl for the Ru(III/II) process in CH3CN/H2O at pH 1.0. The E1/2-pH diagram reveals the intercrossing of Ru(II/III) and Os(II/III) processes at around pH 5.5. Therefore, the intramolecular electron transfer can be controlled by pH. Proton-gated electron rectifying effect was observed in this Ru-Os dinuclear complex.
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