The ligand 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tpp) can be used to bind to one or two metal centers. When this ligand is bound in a tridentate fashion to a single metal, three remote nitrogens remain, which are uncoordinated. Methylation of one of the pyridine nitrogens is possible in high yield to form a covalently coupled viologen. This viologen functions as an electron acceptor to form the basis of a molecular dyad composed of a light absorber–electron acceptor framework. Two such dyads have been synthesized utilizing the other polypyridine ligands 2,2′-bipyridine (bpy) and 2,2′:6′,2″-terpyridine (tpy). The spectroscopic, electrochemical and photochemical properties of these dyads, [Ru(tpy)(Metpp)] 3+ and [Ru(bpy)(Metpp)(CH 3CN)] 3+, as well as the unmethylated analogs, [Ru(tpy)(tpp)] 2+ and [Ru(bpy)(tpp)(CH 3CN)] 2+, have been studied (Metpp, 2-[2-(1-methylpyridinium)]-3,5,6-tris(2-pyridyl)pyrazine). Electrochemically, in the unmethylated complexes, we observe an Ru(II)/Ru(III) oxidation and a tpp/tpp − reduction, which is localized on the pyrazine portion of tpp. On methylation, the ruthenium metal becomes slightly harder to oxidize and a new reduction appears prior to the reduction of the pyrazine ring of the Metpp ligand. This can be attributed to the reduction of the viologen portion of Metpp. Optical excitation of the methylated complex is similar to that of the unmethylated species, with the lowest lying spectroscopically accessible excited state involving Ru(dπ)→tpp(π *) charge transfer with the acceptor orbital being largely localized on the pyrazine portion of the tpp ligand. The lowest unoccupied molecular orbital in the methylated complexes resides on the viologen portion of the Metpp ligand, making these complexes light absorber–electron acceptor dyads.