Photophysics of bis-bipyridyl complexes of ruthenium(II) with triphenylphosphine

We studied the spectral-luminescent characteristics of the luminescence of mixed-ligand polypyridine-phosphine complexes of ruthenium(II) cis-[Ru(bpy)2(PPh3)X](BF4)n with ligands 2,2′-bipyridyl (bpy) and triphenylphosphine (PPh3) and X = Cl−, Br−, CN−, NO2−, NH3, MeCN, pyridine (py), 4-aminopyridine (pyNH2), and 4,4′-bipyridyl (4,4′-bpy) in a 4: 1 EtOH-MeOH alcoholic mixture at 77 K. The radiative and nonradiative deactivation rate constants of the lowest electronically excited state of the complexes are determined. We find that triphenylphosphine has a greater effect on the photophysical characteristics of ruthenium(II) complexes compared to π-acceptor strong-field ligands, such as MeCN, CN−, and NO2−. At the same time, the characteristics of complexes cis-[Ru(bpy)2(PPh3)X]n+ considerably depend on the nature of the second monodentate ligand X, which is coordinated to ruthenium(II), and correlate with its position in the spectrochemical series of ligands.