Although various reactions involved in photoexcited states of polypyridyl ruthenium(II) complexes have been extensively studied, photoisomerization of the complexes is very rare. We report the first illustration of stoichiometric photoisomerization of trans-[Ru(tpy)(pynp)OH(2)](2+) (1a) [tpy = 2,2':6',2''-terpyridine; pynp = 2-(2-pyridyl)-1,8-naphthyridine] to cis-[Ru(tpy)(pynp)OH(2)](2+) (1a') and the isolation of 1a and 1a' for X-ray crystallographic analysis. Polypyridyl ruthenium(II) aquo complexes are attracting much attention related to proton-coupled electron transfer and water oxidation catalysis. We demonstrate that the photoisomerization significantly controls the redox reactions and water oxidation catalyses involving the ruthenium(II) aquo complexes 1a and 1a'.

The catalytic activity of [Ru(tpy)(bpy)OH(2)](2+) (tpy = 2,2':6',2''-terpyridine and bpy = 2,2'-bipyridine) increased by a 4'-substituted ethoxy group on the tpy ligand by more than one order of magnitude to give 1.1 × 10(-1) s(-1) of catalyst turnover frequency, which is comparable with the hitherto-reported champion data.

A ligation of Ru(tpy)Cl3 (tpy = 2,2':6',2"-terpyridine) with 2-(2-pyridyl)-1,8-naphthyridine) (pynp) in the presence of LiCl gave distal-[Ru(tpy)(pynp)Cl](+) (d-1Cl) selectively, whereas the ligation gave proximal-[Ru(tpy)(pynp)OH2](2+) (p-1H2O) selectively in the absence of halide ions. (The proximal/distal isomers were defined by the structural configuration between the 1,8-naphthyridine moiety and the aquo or chloro ligand.) An aquation reaction of d-1Cl quantitatively afforded distal-[Ru(tpy)(pynp)OH2](2+) (d-1H2O) in water, and d-1H2O is quantitatively photoisomerized to p-1H2O. The mechanism of the photoisomerization was investigated by transient absorption spectroscopy and quantum chemical calculations. The temperature dependence of the transient absorption spectral change suggests existence of the thermally activated process from the (3)MLCT state with the activation energy (ΔE = 49 kJ mol(-1)), which is close to that (41.7 kJ mol(-1)) of the overall photoisomerization reaction. However, quantum chemical calculations suggest another activation process involving the conformational change of the pentacoordinated distal structure to the proximal structure. Quantum chemical calculations provide redox potentials and pK(a) values for proton-coupled electron transfer reactions from Ru(II)-OH2 to Ru(IV)═O in good agreement with experiments and provide an explanation for mechanistic differences between d-1H2O and p-1H2O with respect to water oxidation. The calculations show that water nucleophilic attack (WNA) on d-[Ru(V)-O](3+) (the ruthenyl oxo species derived from d-1H2O, calculated ΔG(‡) of 87.9 kJ/mol) is favored over p-[Ru(V)-O](3+) (calculated ΔG(‡) of 104.6 kJ/mol) for O-O bond formation. Examination of the lowest unoccupied molecular orbitals in d- and p-[Ru(V)-O](3+) indicates that more orbital amplitude is concentrated on the [Ru-O] unit in the case of d-[Ru(V)-O](3+) than in the case of p-[Ru(V)-O](3+), where some of the amplitude is instead delocalized over the pynp ligand, making this isomer less electrophilic.

Synthesis, crystal structure, solution and spectroscopic properties, and hydrogen-evolving activity of [K(18-crown-6)][Pt(II)(2-phenylpyridinato)Cl 2 ]