Controlled Assembly of Ru-Containing Polyoxometalates for Photocatalytic Activity of the Primary Amine Coupling Reaction

Three Ru-induced structural interconversion polyoxometalates (POMs), Na₁₃H₅[Ru₄(H₂O)₂(Cl)₂(WO₂)₄(AsW₉O₃₃)₄]·43H₂O (1), K₅Na₉H₈[Ru₂(WO₂)₄(AsW₉O₃₃)₄]·50H₂O (2), and KNa₁₃H₁₄[(WO₂)₄(AsW₉O₃₃)₄]·34H₂O (3), were successfully synthesized and thoroughly characterized. Interconversion of structures was accomplished by changing the number of active sites for compounds 1-3. All three compounds contain one {As₄W₄₀O₁₄₀} unit, showing similar structural characteristics except for the active center number (Ru). Interestingly, compound 1 [turnover number (TON)= 486; turnover frequency (TOF)= 20 h^-1] showed highly efficient photocatalysis in achieving oxidative coupling of primary amines. Compound 2 (TON = 406, TOF = 17 h^-1) was also found to promote the oxidative coupling with relatively poor efficiency; however, compound 3 (TON = 178; TOF = 7.4 h^-1) had no obvious contribution to the coupling reaction system, and a chain of evidence indicates that the catalytic performances are strongly dependent on element contents of active sites. Furthermore, the Ru-containing POM-based photocatalysts are conveniently recyclable and reusable during the photocatalytic processes. This study demonstrates the possibility of tuning the catalytic efficiency and stability of POM-based photocatalysts by well designing and controlling their structures. The possible reaction mechanism for the photocatalysis synthesis of imine product is also proposed based on experimental studies.