Ruthenium(II) complexes containing 8-(dimethylphosphino)quinoline (Me(2)Pqn): preparation,crystal structures,and electrochemical and spectroscopic properties of [Ru(bpy or phen)(3)(-)(n)(Me(2)Pqn)(n)](PF(6))(2) (bpy = 2,2'-bipyridine; phen = 1,10-phenanthroline; n = 1, 2, or 3)

Several new ruthenium(II) complexes containing 8-(dimethylphosphino)quinoline (Me(2)Pqn) were synthesized, and their structures and electrochemical/spectroscopic properties have been investigated. In addition to the mono(Me(2)Pqn) complex Ru(bpy or phen)(2)(Me(2)Pqn)](PF(6))(2) (1 or 1'; bpy = 2,2'-bipyridine; phen = 1,10-phenanthroline), the geometrical isomers trans(P)- and C(1)-Ru(bpy)(Me(2)Pqn)(2)](PF(6))(2) (tP-2 and C(1)-2) and mer- and fac-Ru(Me(2)Pqn)(3)](PF(6))(2) (m-3 and f-3) were also selectively synthesized and isolated. It was found that complexes tP-2 and m-3 were converted quantitatively to the corresponding C(1)-2 and f-3 isomers, respectively, by irradiation of light corresponding to the MLCT transition energy. The strong trans influence of the Me(2)P- donor group of Me(2)Pqn was confirmed by the X-ray structural analyses for 1, tP-2, m-3, and f-3. Cyclic voltammetry of a series of complexes, Ru(bpy)(3)](PF(6))(2), 1, C(1)-2, and f-3, exhibited a reversible one-electron oxidation wave and two or three one-electron reduction waves. The oxidation potentials of the complexes gave a large positive shift with increasing number of coordinated Me(2)Pqn molecules, indicating a larger pi-acceptability of the Me(2)P- group compared with bpy or qn. Complex f-3 in EtOH/MeOH (4:1) glass at 77 K exhibited an intense long-lived (tau = 920 microseconds) emission arising from the quinoline-based (3)(pi-pi) excited state. In contrast, the mixed-ligand complexes 1, 1', and C(1)-2 showed a characteristic dual emission, giving a double-exponential emission decay, and the dual emission originates from both the bpy-based (3)MLCT and the quinoline-based (3)(pi-pi) emitting states.