Coordination cages with intrinsic enzyme-like activity are a class of promising catalysts for improving the efficiency of organic reactions.We present herein a viable strategy to conveniently construct multimetallic a...Coordination cages with intrinsic enzyme-like activity are a class of promising catalysts for improving the efficiency of organic reactions.We present herein a viable strategy to conveniently construct multimetallic active sites into a coordination cage via self-assembly of a pre-formed sulfonylcalix[4]arene-based tetranuclear copper(II)precursor and an amino-functionalized dicarboxylate linker.The cage exhibits a“defective”,partially open cylindrical structure and features coordinatively labile dimetallic Cu(II)sites.Modulated by this unique inner cavity environment,promising catalytic activity toward selective oxidation of primary alcohols to carboxylic acids at room temperature is achieved.Mechanistic studies reveal that the coordinatively labile dimetallic Cu(II)sites can efficiently capture and activate the substrate and oxidant to catalyze the reaction,while the confined nano-cavity environment modulates substrate binding and enhances the catalytic turnover.This study provides a new approach to designing biomimetic multifunctional coordination cages and environmentally friendly supramolecular catalysts.展开更多
基金supported by the National Natural Science Foundation of China(21673239,92061202,U22A20387)the Fujian Science and Technology Project(2020L3022)+2 种基金the Science and Technology Service Network Initiative(STS)Foundation of Fujian Provincial Department of Science and Technology(2021T3004)the financial support provided by the National Science Foundation(CHE-1800354)the South Dakota Governor’s Office of Economic Development through the Center for Fluorinated Functional Materials(CFFM)。
文摘Coordination cages with intrinsic enzyme-like activity are a class of promising catalysts for improving the efficiency of organic reactions.We present herein a viable strategy to conveniently construct multimetallic active sites into a coordination cage via self-assembly of a pre-formed sulfonylcalix[4]arene-based tetranuclear copper(II)precursor and an amino-functionalized dicarboxylate linker.The cage exhibits a“defective”,partially open cylindrical structure and features coordinatively labile dimetallic Cu(II)sites.Modulated by this unique inner cavity environment,promising catalytic activity toward selective oxidation of primary alcohols to carboxylic acids at room temperature is achieved.Mechanistic studies reveal that the coordinatively labile dimetallic Cu(II)sites can efficiently capture and activate the substrate and oxidant to catalyze the reaction,while the confined nano-cavity environment modulates substrate binding and enhances the catalytic turnover.This study provides a new approach to designing biomimetic multifunctional coordination cages and environmentally friendly supramolecular catalysts.
