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 ph...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.展开更多
基金the financial support of the National Natural Science Foundation of China(NSFCgrant nos.21961004,52002089,21531006,21773163)the China Postdoctoral Science Foundation(grant no.2020M670525).
文摘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.
