O. Kohle, S. Ruile, M. Grätzel
Jul 31, 1996
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Inorganic Chemistry
Abstract
The synthesis and properties of several complexes of Ru(II) containing 4,4‘-dicarboxy-2,2‘-bipyridine (dcbpyH2), 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (bmipy), or 2,6-bis(1-methylbenzimidazol-2-yl)-4-phenylpyridine (ph-bmipy), and monodentate ligands (X- = Cl-, I-, NCS-, NCSe-, CN-) are reported. The introduction of the ambident ligands X- = NCS-, NCSe-, and CN- into the coordination sphere of [Ru(bmipy)(dcbpy)I]- and cis-Ru(dcbpyH2)2Cl2 has been studied in situ via 1H and 13C NMR spectroscopy using 13C-enriched ligands X-. Introduction of thiocyanate and selenocyanate initially yields the two possible linkage isomers in comparable amounts; prolonged reaction time converts the S-bound isomer and the Se-bound isomer to the N-bound isomers. The isoselenocyanate complex decomposes rapidly, yielding the cyano complex under loss of Se. The N-bound isothiocyanato complex K[Ru(bmipy)(dcbpy)(NCS)] was found to be an efficient sensitizer for nanocrystalline TiO2; the incident monochromatic photon-to-current e...