The application of coordination polymers(CPs)as a platform to control the arrangement of olefin-containing ligands to produce cyclobutane derivatives by[2+2]photocycloaddition reactions is a highly regioselective and ...The application of coordination polymers(CPs)as a platform to control the arrangement of olefin-containing ligands to produce cyclobutane derivatives by[2+2]photocycloaddition reactions is a highly regioselective and stereoselective approach.However,current research is mainly focused on mono-olefin and di-olefin ligand-based CPs,and research on the photocycloaddition of multi-olefin ligand-based CPs,which will greatly enrich the chemistry of cyclobutane isomers,is still lacking.Herein,we present a strategy to fine-tune the orientation and distance of a triene ligand,1,3,5-tri-4-pyridyl-1,2-ethenylbenzene(tpeb),which is accomplished by carboxylic acid and metal ion co-driven assembly of six kinds of CPs.Five kinds of arrangements of tpeb ligands were realized and the[2+2]photocycloadditions of these CPs under UV light irradiation were precisely controlled to produce di-and tri-cyclobutanes,which were monitored by proton nuclear magnetic resonance(1H NMR)and X-ray diffraction(XRD).This work not only widens the synthetic scope of multi-cyclobutanes and their derivatives but also provides a reference for the precise control of the functional groups of organic molecules in the frameworks of CPs.展开更多
As important halogenating and oxidant agents,the synthesis and utilization of interhalogens are plagued by their purity problem,strong volatility and high reactivity.Herein,a flexible Cd-based metal-organic framework(...As important halogenating and oxidant agents,the synthesis and utilization of interhalogens are plagued by their purity problem,strong volatility and high reactivity.Herein,a flexible Cd-based metal-organic framework(MOF),{[Cd(1,4-bdc)(4-bpa)]·DMF}_(n)(1,where 4-bpa=1,2-bis(4-pyridyl)acetylene),was prepared and its corresponding activation species,[Cd(1,4-bdc)(4-bpa)]_(n)(2),with moderate pore size and shape,acting as a crystal vessel,was applied to synthesize and store pure interhalogens.The synthesis of interhalogen was realized by quantitive transformation of halogen molecules incorporated in the pores of 2,which was confirmed by single-crystal X-ray diffraction and other structural characterizations.The embedded interhalogen molecules were stabilized by their interactions with the inner groups of the porous framework of 2 and released in polar solvent and utilized in iodocyclization of organic alcohols with high selectivity.This work not only opens a new door to the synthesis of pure interhalogens but also demonstrates powerful applications of MOF crystal vessels in realizing classic but important inorganic and organic reactions.展开更多
基金the National Natural Science Foundation of China(22271203 and 21531006)the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry(KF2021005)the Collaborative Innovation Centre of Suzhou Nano Science and Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutions,and the Project of Scientific and Technologic Infrastructure of Suzhou(SZS201905)for financial support.
文摘The application of coordination polymers(CPs)as a platform to control the arrangement of olefin-containing ligands to produce cyclobutane derivatives by[2+2]photocycloaddition reactions is a highly regioselective and stereoselective approach.However,current research is mainly focused on mono-olefin and di-olefin ligand-based CPs,and research on the photocycloaddition of multi-olefin ligand-based CPs,which will greatly enrich the chemistry of cyclobutane isomers,is still lacking.Herein,we present a strategy to fine-tune the orientation and distance of a triene ligand,1,3,5-tri-4-pyridyl-1,2-ethenylbenzene(tpeb),which is accomplished by carboxylic acid and metal ion co-driven assembly of six kinds of CPs.Five kinds of arrangements of tpeb ligands were realized and the[2+2]photocycloadditions of these CPs under UV light irradiation were precisely controlled to produce di-and tri-cyclobutanes,which were monitored by proton nuclear magnetic resonance(1H NMR)and X-ray diffraction(XRD).This work not only widens the synthetic scope of multi-cyclobutanes and their derivatives but also provides a reference for the precise control of the functional groups of organic molecules in the frameworks of CPs.
基金the National Natural Science Foundation of China(No.22271203)the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry,China(No.KF2021005)+1 种基金the Collaborative Innovation Center of Suzhou Nano Science and Technology,Chinathe Priority Academic Program Development of Jiangsu Higher Education Institutions,China,and the Project of Scientific and Technologic Infrastructure of Suzhou,China(No.SZS201905)for financial support.
文摘As important halogenating and oxidant agents,the synthesis and utilization of interhalogens are plagued by their purity problem,strong volatility and high reactivity.Herein,a flexible Cd-based metal-organic framework(MOF),{[Cd(1,4-bdc)(4-bpa)]·DMF}_(n)(1,where 4-bpa=1,2-bis(4-pyridyl)acetylene),was prepared and its corresponding activation species,[Cd(1,4-bdc)(4-bpa)]_(n)(2),with moderate pore size and shape,acting as a crystal vessel,was applied to synthesize and store pure interhalogens.The synthesis of interhalogen was realized by quantitive transformation of halogen molecules incorporated in the pores of 2,which was confirmed by single-crystal X-ray diffraction and other structural characterizations.The embedded interhalogen molecules were stabilized by their interactions with the inner groups of the porous framework of 2 and released in polar solvent and utilized in iodocyclization of organic alcohols with high selectivity.This work not only opens a new door to the synthesis of pure interhalogens but also demonstrates powerful applications of MOF crystal vessels in realizing classic but important inorganic and organic reactions.
