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
A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2...A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2·4 H2 O under solvothermal conditions. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction(PXRD) and thermogravimetric analyses(TGA). Single-crystal X-ray diffraction analyses reveal that complex 1 consists of a 3 D network with one-dimensional(1 D) channels. Moreover, 1 exhibits strong luminescent emission in solid state at room temperature. Fluorescence quenching was observed when treating complex 1 with picric acid(PA), 2,4-dinitrophenylhydrazine(2,4-DNPH) and p-nitroaniline(p-NA), revealing that the as-synthesized complex could be used as a luminescence sensor for the detection of PA, 2,4-DNPH and p-NA.展开更多
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.
基金supported by the Natural Science Foundation of Shaanxi Province(2018JQ2079,2018JQ2040,2018JM2055)
文摘A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2·4 H2 O under solvothermal conditions. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction(PXRD) and thermogravimetric analyses(TGA). Single-crystal X-ray diffraction analyses reveal that complex 1 consists of a 3 D network with one-dimensional(1 D) channels. Moreover, 1 exhibits strong luminescent emission in solid state at room temperature. Fluorescence quenching was observed when treating complex 1 with picric acid(PA), 2,4-dinitrophenylhydrazine(2,4-DNPH) and p-nitroaniline(p-NA), revealing that the as-synthesized complex could be used as a luminescence sensor for the detection of PA, 2,4-DNPH and p-NA.
