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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.

Various substituted dirhodium tetraformamidinate complexes, Rh(2)(R-form)(4) (R = p-CF(3), p-Cl, p-OCH(3), m-OCH(3); form = N,N'-diphenylformamidinate), and the new complex Rh(2)(tpgu)(4) (tpgu = 1,2,3-triphenylguanidinate) have been investigated as potential agents for the photoremediation of saturated halogenated aliphatic compounds, RX (R = alkyl group). The synthesis and characterization of the complexes is reported, and the crystal structure of Rh(2)(tpgu)(4) is presented. The lowest energy transition of the complexes is observed at approximately 870 nm and the complexes react with alkyl chlorides and alkyl bromides under low energy irradiation (lambda(irr) > or = 795 nm), but not when kept in the dark. The metal-containing product of the photochemical reaction with RX (X = Cl, Br) is the corresponding mixed-valent Rh(2)(II,III)X (X = Cl, Br) complex, and the crystal structure of Rh(2)(p-OCH(3)-form)(4)Cl generated photochemically from the reaction of the corresponding Rh(2)(II,II) complex in CHCl(3) is presented. In addition, the product resulting from the dimerization of the alkyl fragment, R(2), is also formed during the reaction of each dirhodium complex with RX. A comparison of the dependence of the relative reaction rates on the reduction potentials of the alkyl halides and their C-X bond dissociation energies are consistent with an outer-sphere mechanism. In addition, the relative reaction rates of the metal complexes with CCl(4) decrease with the oxidation potential of the dirhodium compounds. The mechanism of the observed reactivity is discussed and compared to related systems.