The extent of metal−ligand orbital mixing and the degree of electronic coupling between [M(bpy)2]2+ fragments linked through a redox active 1,4-dihydroxy-2,5-bis(pyrazol-1‘-yl)benzene (p-L) bridge is described, where M is Os or Ru and bpy is 2,2‘-bipyridyl. This is the first reported example of osmium and ruthenium/osmium metals linked across a 1,4-dioxolene bridge. In fast scan cyclic voltammetry, the redox processes are reversible and four distinct one-electron processes are observed for the bridge and metal centers in the homo- and hetero-dinuclear complexes. The potential at which the first oxidation step occurs does not depend on the identity of the metal center. UV/vis spectroelectrochemistry, together with resonance Raman spectroscopy, suggests that the first two oxidation steps occur on the bridging ligand. For all complexes, an orbital mixing gradient occurs; metal−ligand orbital mixing increases in the order HQ ≪ SQ < Q (HQ is the reduced hydroquinone bridge, SQ the semiquinone, and Q the quinon...