Transient resonance Raman spectra have been acquired for the chromophore-quencher complexes fac-[(bpy)-Re(I)(CO)3(MQ+)]2+ and cis-[(bpy)2Os(II)(CO)(MQ+)]3+ (MQ+ is monoquat, N-methyl-4,4’-bipyridinium cation; bpy is 2,2’-bipyridine) following metal-to-ligand charge-transfer excitation. The transient spectra verify that bpy.- --> MQ+ intramolecular electron transfer occurs (tau < 7 ns) with the excited electron residing ultimately on the monoquat ligand. By comparison to vibrational data for biphenyl, 4,4’-bipyridine, N,N’-dihydro-4,4’-bipyridinium dication, and methyl viologen (paraquat) and their corresponding, one-electron reduced forms, it can be inferred that, in the MQ+-based MLCT excited state, the electron is delocalized over the entire ligand and the two pyridyl rings assume a coplanar geometry.