Folding encapsulation toward Lindqvist polyoxometalates within adaptive coordination cages for catalysis  

作　　者：Ying-Mei Zhong Jin-Jin Xuan Xujie Qin Han Xiao Zi-Jun Xia Li-Peng Zhou Xiao-Qing Guo Yu-Hang Hu Lu Zhang Chunsen Li Li-Xuan Cai Qing-Fu Sun 

机构地区：[1]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [2]University of Chinese Academy of Sciences,Beijing 100049,China [3]College of Chemistry and Materials Science,Fujian Normal University,Fuzhou 350007,China

出　　处：《Science China Chemistry》2025年第2期561-569,共9页中国科学(化学英文版)

基　　金：supported by the National Key Research and Development Program of China(2022YFA1503300,2021YFA1500400);the National Natural Science Foundation of China(22171262,22171264,22201285);the Science Foundation of Fujian Province(2021J01516,2021J02016).

摘　　要：In nature,enzymes at specific folded conformations exhibit high substrate complementarity,enabling them to efficiently and selectively catalyze biochemical reactions.Inspired by enzymes,coordination cages with conformational dynamics have been designed and are receiving increasing attention due to their versatile applications in allosteric guest binding and catalysis.We present here two enzyme-mimicking adaptive macrocycle-based coordination cages,Pd_(2)L_(2)^(1) and Pd_(2)L_(2)^(2),from macrocycle-based ligands(L^(1) and L^(2))and the encapsulation and stabilization of Lindqvist polyoxometalates anions M6O192−(M=W or Mo)in neutral aqueous solution.X-ray crystallographic studies have verified the formation of 1:1 host-guest complexes of two Pd_(2)L_(2) cages and the W6O192−anion,via an induced-fit folding mechanism.Compared with the free host,Pd_(2)L_(2)^(1) exhibited an induced-fit semi-folded conformation in the inclusion complex,while Pd_(2)L_(2)^(2) adopted an induced-fit fully-folded conformation.Moreover,the Mo_(6)O_(19)⊂Pd_(2)L_(2) host-guest complexes demonstrate high yield and selectivity in the oxidative decontamination reaction of the sulfur mustard simulant,2-chloroethyl ethyl sulfide.This work not only sheds light on the importance of conformational adaptability in enzyme-like systems but also paves the way for protecting labile POM clusters via host-guest encapsulation toward enhanced catalytic performance in aqueous solution.

关 键 词：coordination cage induced-fit POLYOXOMETALATES host-guest chemistry supramolecular catalysis 

分 类 号：O641.4[理学—物理化学] O643.36[理学—化学]