New dinuclear asymmetric ruthenium complexes of the type [(bpy)(2)Ru(5-CNphen)Ru(NH3)(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(NH3)(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(NH3)(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 RuII --> 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.