Ground-State Properties and Excited-State Reactivity of 8-Quinolate Complexes of Ruthenium(II).

Abstract

In an effort to explore new systems with highly reducing excited states, we prepared a series of Ru(II) complexes of the type Ru(L)(2)quo(+) (L = bpy (2,2'-bipyridine), phen (1,10-phenanthroline), dmphen (4,7-dimethyl-1,10-phenanthroline), tmphen (3,4,7,8-tetramethyl-1,10-phenanthroline); quo(-) = 8-quinolate) and investigated their photophysical and redox properties. The absorption and emission spectra of the Ru(L)(2)quo(+) are significantly red-shifted relative to those of the parent complexes Ru(L)(3)(2+), with emission maxima in the 757-783 nm range in water. The Ru(L)(2)quo(+) systems are easily oxidized with E(1/2)(Ru(III/II)) values ranging from +0.62 to +0.70 V vs NHE, making the emissive Ru --> phen MLCT (metal-to-ligand charge transfer) excited states (E(00) approximately 1.95 eV in CH(3)CN) of the Ru(L)(2)quo(+) complexes significantly better reducing agents than the MLCT states of the parent Ru(L)(3)(2+) complexes. Emission lifetimes of 17.0 and 32.2 ns were measured for Ru(phen)(2)quo(+) in water and acetonitrile, respectively, and 11.4 ns for Ru(bpy)(2)quo(+) in water. Transient absorption results are consistent with the formation of reduced methyl viologen upon Ru(phen)(2)quo(+) excitation with visible light in water. The possibility of observing the Marcus inverted region in the forward bimolecular electron transfer reaction from the highly reducing Ru(phen)(2)quo(+) excited state was explored with neutral electron acceptors with reduction potentials ranging from +0.25 to -1.15 V vs NHE.