The synthetic chemistry of substituted 4,4'-azobis(phenylcyanamide) ligands was investigated, and the complexes [{Ru(tpy)(bpy)}(2)(mu-L)][PF6](2), where L = 2,2':5,5'-tetramethyl-4,4'-azobis(phenylcyanamido) (Me4adpc(2)), 2,2'-dimethyl-4,4'-azobis(phenylcyanamido) (Me(2)adpc(2)), unsubstituted (adpc2), 3,3'-dichloro-4,4'-azobis(phenylcyanamido) (Cl(2)adpc(2)), and 2,2':5,5'-tetrachloro-4,4'-azobis(phenylcyanamido) (Cl(4)adpc(2)), were prepared and characterized by cyclic voltammetry and visnear-IR (NIR) and IR spectroelectrochemistry. The room temperature electron paramagnetic resonance spectrum of [{Ru(tpy)(bpy)}(2)(mu-Me(4)adpc)](3+) showed an organic radical signal and is consistent with an oxidation-state description [Ru-II, Me(4)adpc, Ru-II](3+), while that of [{Ru(tpy)(bpy)}(2)(mu-Cl(2)adpc)](3+) at 10 K showed a low-symmetry Ru-III signal, which is consistent with the description [Ru-III, Cl(2)adpc(2), Ru-II](3+). IR spectroelectrochemistry data suggest that [{Ru(tpy)(bpy)}(2)(mu-adpc)](3+) is delocalized and [{Ru(tpy)(bpy)}(2)(mu-Cl(2)adpc)](3+) and [{Ru(tpy)(bpy)}(2)(mu-Cl(4)adpc)](3+) are valence-trapped mixed-valence systems. A NIR absorption band that is unique to all [{Ru(tpy)(bpy)}(2)(mu-L)](3+) complexes is observed; however, its energy and intensity vary depending on the nature of the bridging ligand and, hence, the complexes oxidation-state description.