Persistence of the three-state description of mixed valency at the localized-to-delocalized transition.

Application of a semiclassical three-state model of mixed valency to complexes of the type Ru(3)(μ(3)-O)(OAc)(6)(CO)(py)-(μ(2)-BL)-Ru(3)(μ(3)-O)(OAc)(6)(CO)(py), where BL = 1,4-pyrazine or 4,4'-bipyridine and py = 4-dimethylaminopyridine, pyridine, or 4-cyanopyridine is described. The appearance of two intervalence charge transfer (IVCT) bands in the near-infrared (NIR) region of the electronic spectra of these complexes is explained well by the three-state model. An important feature of the three-state model is that the IVCT band evolves into two bands: one that is metal-to-bridging-ligand-charge-transfer (MBCT) in character and another that is metal-to-metal-charge-transfer (MMCT) in character. The three-state model also fully captures the observed spectroscopic behavior in which the MBCT transition increases in energy and the MMCT band decreases in energy with increasing electronic communication in a series of mixed valence ions. The appearance of both the MBCT and MMCT bands is found to persist as coalescence of infrared (IR) vibrational spectra suggest a ground state delocalized on the picosecond time scale. The solvent and temperature dependence of the MBCT and MMCT electronic transitions defines the mixed valence complexes reported here as lying on the borderline of delocalization.