Polyoxovanadate-Based Metal–Organic Frameworks with Dual Active Sites for the Synthesis of p-Benzoquinones

p-Benzoquinones are important organic intermediates in the synthesis of biopharmaceuticals and fine chemicals. In this study, two crystalline 3D polyoxovanadate-based metal–organic frameworks, H[Cu(tpi)₂]{Cu₂V₇O₂₁}·H₂O (1, tpi = C₁₈N₅H₁₃) and [Co(Htpi)₂]{V₄O₁₂} (2, Htpi = C₁₈N₅H₁₄), were synthesized, which as heterogeneous catalysts showed excellent catalytic activities for the synthesis of p-benzoquinones. Both compounds were characterized by IR, UV–vis diffuse reflectance spectroscopy, TG, XPS, X-ray diffraction, etc. In 1, {Cu₂V₇} clusters are connected together by copper cations and 1D Cu–organic coordination chains to yield a 3D polyoxometalate-based metal–organic framework (POMOF); in 2, adjacent 2D bimetallic oxide layers, constructed from 1D polyoxovanadate chains and cobalt ions, are further connected by 1D Co–organic coordination chains to form a 3D POMOF. Noteworthily, in the synthesis of trimethyl-p-benzoquinone, the key intermediate of vitamin E, using 2,3,6-trimethylphenol as the model substrate, the turnover frequency values for compounds 1 and 2 can, respectively, reach 607 and 380 h^–1 in 8 min. Furthermore, both compounds demonstrated excellent recyclability and structural stability, characterized by PXRD and IR. The catalytic mechanism reveals that both the homolytic radical mechanism and heterolytic oxygen atom transfer mechanism are involved.