{Ru(C6H6)}‐Decorating Heteropolymolybdate for Highly Activity Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde

Abstract 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.