Binuclear ruthenium complexes with two Ru(bpy)₂(PyCHN) units, where bpy = 2,2′-bipyridine and PyCHN = N-2-pyridylmethylene, linked together either directly or via spacers of variable length and nature have been prepared and characterizated. Electrochemical studies revealed that the comproportionation constant K_c clearly decreased with an increase in the number of phenyl rings. While inserting oxygen atom between the two phenyl rings decreased the K_c value, interruption of saturated CH₂ groups increased K_c from 2.7 × 10⁵ to 5.8 × 10⁵. The binuclear ruthenium complex containing the saturated –OCH₂CH₂O– fragment between the two phenyl groups also gave a large K_c (1.2 × 10⁴), indicating that interruption within the bridge played a significant role in influencing ΔE and K_c for the dinuclear ruthenium complexes. These results demonstrated that the Schiff-base bridging ligands were particularly efficient for mediating the metal–metal coupling and approached molecular wire behavior. X-Ray crystal structure analyses of the free ligand BL₆ and one of the ruthenium complexes, 1, are also reported.