Polyoxometalates (POMs) are widely applied as tuneable and versatile catalysts for a variety of oxidation reactions in an aqueous/organic two-phase system. However, the practical applications of POMs-based biphasic catalysis are hampered by low space-time yields and mass-transport limitation between two layers due to extremely low solubility of the organic reactants in the aqueous phase. Here, we first introduced β-cyclodextrin (β-CD) as an inverse phase transfer agent and a supramolecular nanoreactor to construct a supramolecular POM inorganic–organic hybrid framework (KCl₄)Na₇[(β-CD)₃(SiW₁₂O₄₀)]·9H₂O {3CD@SiW₁₂} for various oxidation catalyses. In contrast to free CD, Keggin [SiW₁₂O₄₀]^4– catalysts, and their mixture, the {3CD@SiW₁₂} catalyst, efficiently catalyze oxidation reactions of alcohol, alkene, and thiophene. A comprehensive strategy of experimental, crystallographic, and density functional theory (DFT) calculations elucidates that the catalytic pathway involved three combined aspects of supramolecular recognition, phase transfer property, and POM catalysis. The strategic combination of supramolecular characteristic and POM-based catalysts to fabricate supramolecular POM hybrid materials opens up new economic and green tuning options, thus paving the way to informed catalyst design.

中文翻译：

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自组装的超分子多金属氧酸盐杂化体系结构作为多功能氧化催化剂

多金属氧酸盐（POM）广泛用作可调节的多用途催化剂，用于水/有机两相系统中的各种氧化反应。然而，由于有机反应物在水相中的溶解度极低，低时空产率和两层之间的传质限制限制了基于POMs的双相催化的实际应用。在这里，我们首先引入β-环糊精（β-CD）作为逆相转移剂和超分子纳米反应器，以构建超分子POM无机-有机杂化骨架（KCl ₄）Na ₇ [（β-CD）₃（SiW ₁₂ O ₄₀）]·9H ₂ O { 3CD @ SiW ₁₂}用于各种氧化催化剂。与游离CD相比，Keggin [SiW ₁₂ O ₄₀ ] ^4–催化剂及其混合物{ 3CD @ SiW ₁₂ }催化剂有效地催化了醇，烯烃和噻吩的氧化反应。实验，晶体学和密度泛函理论（DFT）计算的综合策略阐明了催化途径涉及超分子识别，相转移性质和POM催化的三个组合方面。超分子特性催化剂和基于POM的催化剂的战略组合，以制造超分子POM杂化材料，开辟了新的经济和绿色调整选择，从而为知情的催化剂设计铺平了道路。