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 [RuíCObCX],,. 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(Me2bpy)(phen)(bpa)](PF6)2'C6Hi4 [C40H43F12N7P2RU, M = 1062.8; Me2bpy = 4J4'-dimethyl-2,2'-bipyridine, phen = 1,10-phenanthroline, bpa = bis(2-pyridyl)amine]: triclinic, space group PI, a = 14.57(3) k,b= 13.50(3) k, c = 12.73(3) Á, a = 68.6(2)°, ß = 63.5(1)°, = 79.8(2)°, V = 2082 Á3, Z = 2. Aspects of the electrochemistry, spectroscopy, and photophysics of the tris-(heteroleptic) species are discussed.

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Irradiation of solutions containing complexes of the type [RuL(CO) 2 Cl 2 ] where L is a 2,2Ј-bipyridine analogue leads to monodecarbonylation and the formation of dimeric ruthenium(II) complexes, [RuL(CO) 2 Cl] 2 , for which two different structures have been established, viz. with a trans disposition of bridging and terminal chlorides [L = di(2pyridyl) ketone] or with CO trans to bridging chlorides (L = 1,10-phenanthroline).

The history of this important set of tools and techniques.

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