Selective synthesis of heteroleptic Pd_(2)A_(3)B-cages:modulating size-preference of supramolecular hosts via endo-functionalization  

作　　者：Wen-Tao Dai Ting-Ting Liu Qixia Bai Zhe Zhang Pingshan Wang Wei Lu Qi Zhang 

机构地区：[1]Key Laboratory of Green Chemistry and Technology of Ministry of Education,College of Chemistry,Sichuan University,Chengdu 610064,China [2]Institute of Environmental Research at Greater Bay Area,Key Laboratory for Water Quality and Conservation of the Pearl River Delta,Ministry of Education,Guangzhou University,Guangzhou 510006,China

出　　处：《Science China Chemistry》2024年第12期4110-4115,共6页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22171192);the“1000-Youth Talents Program”,the Science&Technology Department of Sichuan Province(2022ZYD0050);the Fundamental Research Funds for the Central Universities。

摘　　要：The size complementarity between a host and a guest is a critical prerequisite for selective molecular recognition.Numerous artificial host systems have been designed to achieve size-selective recognition and chemical transformations.However,the inherent challenge lies in the fixed selectivity governed by a size-exclusion mechanism dictated by the host's structure.Modulating the selectivity necessitates structural modifications of hosts.Examples of host systems with modifiable sizeselectivity are rare.In this study,we present an approach to modulating guest-selectivity via endo-functionalization of supramolecular cavities.Heteroleptic Pd_(2)A_(3)B-cages are constructed with a Pd_(2)A_(3)precursor or directly from palladium ions and relevant ligands.Furthermore,the simultaneous and selective formation of multiple hetero-cages was achieved by simply mixing PdIIand the free ligands in a one-pot reaction.The fidelity of the assembly process relies on cooperative steric control at the periphery and within the cavity of the hetero-cages,respectively.The central steric group also functions as the endohedral moiety.Variations of the endohedral groups facilitate facile and modular derivatization of the microenvironment within the cages,enabling the fine-tuning of guest binding affinities as evidenced by titration experiments.This strategy offers a new solution for the development of customized host structures.

关 键 词：endo-functionalization heteroleptic assemblies host-guest chemistry size-selectivity metal-ligand supramolecular structures 

分 类 号：O641.3[理学—物理化学]