文献类型：期刊文献

英文题名：Catenated Cages Mediated by Enthalpic Reaction Intermediates

作者：Xu, Shijun[1];Li, Pan[2];Li, Zi-Ying[1];Yu, Chunyang[2];Liu, Xiaoyun[1];Liu, Zhiqiang[3];Zhang, Shaodong[2]

机构：[1]East China Univ Sci & Technol, Key Lab Specially Funct Polymer Mat & Related Tec, Minist Educ, Shanghai 20023Z, Peoples R China;[2]Shanghai Jiao Tong Univ, Shanghai Key Lab Elect Insulat & Thermal Aging, Frontiers Sci Ctr Transformat Mol, Sch Chem & Chem Engn, Shanghai 200240, Peoples R China;[3]Zhejiang Univ Technol, Natl & Local Joint Engn Res Ctr Biomfg Chiral Che, Hangzhou 310014, Peoples R China

年份：2021

卷号：3

期号：7

起止页码：1838

外文期刊名：CCS CHEMISTRY

收录：WOS:【ESCI(收录号:WOS:000794212600007)】；

基金：This study was supported by the National Natural Science Foundation of China (key program 21890733) and the Shanghai Natural Science Foundation (no. 18ZR1420800).

语种：英文

外文关键词：cage; catenane; enthalpic intermediate; interlocked cages; supramolecular chemistry

摘要：Catenated cages are generally considered thermodynamically more stable than their constituent monomeric cages. However, the catenation mechanism is yet to be elucidated; it would require systematic investigation into the structural effects of the building blocks, their enthalpic and entropic contributions, and the effect of solvents. By inspecting these factors, we rationalized some design principles for the efficient construction of catenated cages. Our study revealed that a steric hindrance linker and a rigid panel led to the formation of an enthalpy-favored encapsulated intermediate before catenation occurred. The stability of this enthalpic intermediate was crucial for cage catenation, as the reactions were otherwise outcompeted by an entropy-favored intermediate. The formation of the latter was facilitated significantly by a flexible panel and solvent molecules that stably resided within the monomeric cage. This study provides a guideline for the elaboration of catenated cages with more sophisticated topologies, which could be extended to other complex supramolecular assemblies.