Fabrication of Polyoxometalate-Based Metal-Organic Frameworks Integrating Paddlewheel Rh₂(OAc)₄ for...

The development of visible-light-responsive, environmentally friendly, and reusable photocatalysts for organic oxidation reactions is of vital significance. Herein, four polyoxometalate-based metal-organic frameworks (POMOFs) were synthesized and systematically characterized by assembling the paddlewheel complex Rh₂(OAc)₄ and various polyoxometalates (POMs). Single-crystal X-ray diffraction analysis revealed that the four POMOFs were isomorphic and possessed rare structural features among the POMOFs, with POMs as nodes and Rh₂(OAc)₄ as linkers. As expected, the activities of the four POMOFs for the photocatalytic oxidative coupling of benzylamine were better than that of Rh₂(OAc)₄ or POMs individually, which was ascribed to the synergistic effect between them, and the intrinsic reasons for the difference in the activity were explained via electrochemical measurements. In particular, the product imine yield reached 96.1% with NaRh-SiW as the catalyst and a turnover number and a turnover frequency of 480.5 and 120.5 h^-1, respectively, while the product yield remained as high as 92% after three repetitions, evidencing its high stability. Moreover, the higher activities of the four POMOFs for the selective epoxidation of various alkenes reaffirm the synergistic effect between Rh₂(OAc)₄ and POMs.