Inorganic Chemistry, Vol.38, No.26, 6187-6192, 1999
Ground-state properties and excited-state reactivity of 8-quinolate complexes of ruthenium(II)
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 similar to 1.95 eV in CH3CN) 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 accepters with reduction potentials ranging from +0.25 to -1.15 V vs NHE.
Keywords:ELECTRON-TRANSFER REACTIONS;MARCUS INVERTED REGION;BINUCLEARPOLYPYRIDYL COMPLEXES;BRIDGED POLYNUCLEAR COMPLEXES;TRANSITION-METAL COMPLEXES;SOLAR-ENERGY CONVERSION;PHOTOINDUCED ELECTRON;STARBURST DENDRIMERS;CHARGE SEPARATION;PHOTOPHYSICAL CHARACTERIZATION