Heteroleptic Ruthenium Complexes With 6-(Ortho-Substituted Phenyl)- 2,2'-Bipyridine Derivatives

Coordination chemistry of 2,2'-bipyridine bearing an ortho-substituted phenyl group at the 6-position, i.e., 6-(o-X-phenyl)-2,2'-bipyridine (MeO-L: X = OMe; Me2N-L: X = NMe2) with [Ru(ttpy)Cl3] (ttpy = 4'- (4-tolyl)-2,2';6',2''-terpyridine) was investigated. The reaction of MeO-L and [Ru(ttpy)Cl3] in the presence of N-methylmorpholine afforded demethylated, O-coordinated complex [Ru(O-L)(ttpy)]+ (O-L: X = O) as well as the cyclometalated, C-coordinated complex [Ru(MeO-L)(ttpy)]+. On the other hand, reaction of Me2N-L and [Ru(ttpy)Cl3] in the presence of N-methylmorpholine afforded only N-coordinated complex [Ru(Me2N-L)(ttpy)]2+. The crystal structures, spectroscopic and redox properties were examined sup- plemented by DFT calculations. The spectroscopic and redox properties of RuN are more or less similar to those of [Ru(ttpy)Cl3]. On the other hand, the properties of RuC and RuO are mutually similar but significantly different from those of RuN. The anionic ligand in RuC and RuO raises the HOMO energy as compared to the neutral ligand in RuN, which is manifested in negatively shifted redox potentials, particularly the oxidation potentials, and thus, the red shift in the visible absorption band. Relevance of these complexes to sensitizers for dye-sensitized solar cells is briefly discussed.