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A new series of panchromatic ruthenium(II) sensitizers derived from carboxylated terpyridyl complexes of tris-thiocyanato Ru(II) have been developed. Black dye containing different degrees of protonation {(C₂H₅)₃NH}[Ru(H₃tcterpy)(NCS)₃] 1, {(C₄H₉)₄N}₂[Ru(H₂tcterpy)(NCS)₃] 2, {(C₄H₉)₄N}₃[Ru(Htcterpy)(NCS)₃] 3, and {(C₄H₉)₄N}₄[Ru(tcterpy)(NCS)₃] 4 (tcterpy = 4,4‘,4‘ ‘-tricarboxy-2,2‘:6‘,2‘ ‘-terpyridine) have been synthesized and fully characterized by UV−vis, emission, IR, Raman, NMR, cyclic voltammetry, and X-ray diffraction studies. The crystal structure of complex 2 confirms the presence of a Ru^IIN6 central core derived from the terpyridine ligand and three N-bonded thiocyanates. Intermolecular H-bonding between carboxylates on neighboring terpyridines gives rise to 2-D H-bonded arrays. The absorption and emission maxima of the black dye show a bathochromic shift with decreasing pH and …