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  • Title: Dinuclear asymmetric ruthenium complexes with 5-cyano-1,10-phenanthroline as a bridging ligand.
    Author: Mellace MG, Fagalde F, Katz NE, Crivelli IG, Delgadillo A, Leiva AM, Loeb B, Garland MT, Baggio R.
    Journal: Inorg Chem; 2004 Feb 09; 43(3):1100-7. PubMed ID: 14753833.
    Abstract:
    New dinuclear asymmetric ruthenium complexes of the type [(bpy)(2)Ru(5-CNphen)Ru(NH(3))(5)](4+/5+) (bpy = 2,2'-bipyridine; 5-CNphen = 5-cyano-1,10-phenanthroline) have been synthesized and characterized by spectroscopic, electrochemical, and photophysical techniques. The structure of the cation [(bpy)(2)Ru(5-CNphen)Ru(NH(3))(5)](4+) has been determined by X-ray diffraction. The mononuclear precursor [Ru(bpy)(2)(5-CNphen)](2+) has also been prepared and studied; while its properties as a photosensitizer are similar to those of [Ru(bpy)(3)](2+), its luminescence at room temperature is quenched by a factor of 5 in the mixed-valent species [(bpy)(2)Ru(II)(5-CNphen)Ru(III)(NH(3))(5)](5+), pointing to the occurrence of intramolecular electron-transfer processes that follow light excitation. From spectral data for the metal-to-metal charge-transfer transition Ru(II) --> Ru(III) in this latter complex, a slight electronic interaction (H(AB) = 190 cm(-1)) is disclosed between both metallic centers through the bridging 5-CNphen.
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