Designed Synthesis of Mononuclear Tris(heteroleptic) Ruthenium Complexes Containing Bidentate Polypyridyl Ligands

A general synthetic methodology is reported for tris(bidentate)ruthenium(II) complexes containing three different polypyridyl ligands, based on the sequential addition of the ligands to the oligomer [Ru(CO)(2)Cl-2](n). The tris(heteroleptic) complexes were characterized by FAB mass spectrometry and NMR spectroscopy. An X-ray crystal structure determination was made for the complex, [Ru(Me(2)bpy)(phen)(bpa)](PF6)(2) . C6H14 [C40H43F12N7P2Ru, M = 1062.8; Me(2)bpy = 4,4'-dimethyl-2,2'-bipyridine, phen = 1,10-phenanthroline, bpa = bis(2-pyridyl)amine]: triclinic, space group , a = 14.57(3) Angstrom, b = 13.50(3) Angstrom, c = 12.73(3) Angstrom, alpha = 68.6(2)degrees, beta = 63.5(1)degrees, gamma = 79.8(2)degrees, V = 2082 Angstrom(3), Z = 2. Aspects of the electrochemistry, spectroscopy, and photophysics of the tris(heteroleptic) species are discussed.