Pore-Directed Solid-State Selective Photoinduced E–Z Isomerization and Dimerization within Metal–Organic Frameworks

作     者：Shu-Li Chen Yan Mi Fei-Long Hu David James Young Jianping Lang Shu-Li Chen;Yan Mi;Fei-Long Hu;David James Young;Jianping Lang

作者机构：Key Laboratory of Chemistry and Engineering of Forest ProductsState Ethnic Affairs CommissionGuangxi Minzu UniversityNanning 530006Guangxi College of ChemistryChemical Engineering and Materials ScienceSoochow UniversitySuzhou 215123Jiangsu College of EngineeringIT and EnvironmentCharles Darwin UniversityDarwin 0909Northern Territory 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2023年第5卷第5期

页      面：1225-1232页

核心收录：

学科分类：07[理学] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：the financial support of the National Natural Science Foundation of China(NSFC grant nos.21961004,52002089,21531006,21773163) the China Postdoctoral Science Foundation(grant no.2020M670525). 

主　　题：pore engineering E–Z photoisomerization photodimerization metal–organic frameworks solid-state reaction 

摘      要：Design and construction of suitable pore microenvironments for selective catalytic reactions of small guest molecules is a major goal for chemists.Herein,we report control of competitive E–Z photoisomerization and photodimerization within porous metal–organic frameworks(MOFs)by fine-tuning the pore microenvironments using different dicarboxylate linkers.MOFs with small pores((E)-X_(MOF_(1))and(E)-X_(MOF_(1))′)favor the photoinduced E–Z isomerization of one encapsulated diaryl alkene substrate while those with large pores(((E)-X)_(2MOF_(2)))prefer the photodimerization of two encapsulated alkene substrates.Both reactions show broad functional group compatibility and proceed stereospecifically in good yields under mild conditions.High local concentration of diaryl alkene ligands and their preorientation within pores facilitate stereoselective dimerization.This pore engineering strategy is applicable to control and create pore microenvironemnts for other photoinduced organic reactions within porous MOFs.