{Ru(C 6 H 6 )}-Decorating Heteropolymolybdate for Highly Activity Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde.

An unclassical structure of {Ru(C 6 H 6 )}-based polyoxometalate, Cs 6 H 4 [Te 2 Mo 12 O 46 {Ru(C 6 H 6 )}] ⋅ 16.5H 2 O (1), has been successfully constructed from {Te 2 Mo 12 O 46 }-type heteropolymolybdate and {Ru(C 6 H 6 )} group, which structure type was discovered for the first time. Compound 1 not only possesses strong light-harvesting ability, but also exhibits high carrier separation efficiency and lower charge transfer resistance. Under visible light irradiation, compound 1 displayed excellent catalytic activity and circularity in the conversion of benzyl alcohol to benzaldehyde (yield=94 %; turnover number=500; turnover frequency=20.8 h -1 ). Finally, the electron paramagnetic resonance measurement and energy level matching analysis provide theoretical basis for the derivation of the reaction mechanism.