The mixed-valence systems meso- and rac-[{M(bPY)(2)}(2)(mu-BL)](5+) {M = Ru, Os; BL = a series of polypyridyl bridging ligands such as 2,3-bis(2-pyridyl)benzoquinoxaline (dpb)} are characterized by multiple intervalence charge transfer (IVCT) and interconfigurational (IC) bands in the mid-infrared and near-infrared (NIR) regions. Differences in the relative energies of the IC transitions for the fully oxidized (+6) states of the osmium systems demonstrate that stereochemical effects lead to fundamental changes in the energy levels of the metal-based d pi orbitals, which are split by spin-orbit coupling and ligand-field asymmetry. An increase in the separation between the IC bands as BL is varied reflects the increase in the degree of electronic coupling through the series of ruthenium and osmium complexes, The increase in the lVCT bandwidths for the former is therefore attributed to the increase in the separation of the three underlying components of the bands. Stark effect measurements reveal small dipole moment changes accompanying lVCT excitation in support of the localized-to-delocalized or delocalized classification for the dinuclear ruthenium and osmium systems.