A series of [Cr (L)(2)(NCS)(2)]X Complexes, where L = 2,2'-bipyridine (bpy) or 4,4'-dimethyl-2,2'-bipyridine (dmb) and X-is, I-, I-3(-), or NO3-, have been prepared for study as redox-inactive surrogates for diisothiocyanatobis-(2,2'-bipyridine-4,4'-dicarboxylic acid)ruthenium(RI) ("N3(+)"). Dilute solution spectra in dichloromethane or acetonitrile of the I- and NO3-salts are the same, but the I- salts show clear evidence of a charge-transfer interaction between the cation and anion in the solid state and in concentrated I- solutions in acetonitrile. X-ray structural determination of the drub complex shows that this interaction is between the I- and one of the dmb ligands. X-ray structural determination of the bpy complex as the I-3(-) salt indicates a similar interaction between one of the bpy ligands, and one of the terminal iodine atoms of the anion. These results have potential implications, in the reduction mechanism of photo-oxidized N3 dye used as a sensitizer in nanocrystalline TiO2-based photogalvanic cells.