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 ?exible 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 con?rmed 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.

中文翻译：

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用于卤间化合物合成的镉基 MOF 晶体容器

卤间化合物作为重要的卤化剂和氧化剂，其合成和利用面临着纯度问题、挥发性强、反应活性高等问题。本文中，柔性Cd基金属有机骨架（MOF），{[Cd(1,4-bdc)(4-bpa)]·DMF}n (1，其中4-bpa = 1,2-bis(制备了4-吡啶基)乙炔)，并应用了其相应的活化物质，[Cd(1,4-bdc)(4-bpa)]n (2)，具有中等孔径和形状，充当晶体容器合成和储存纯卤间化合物。卤间化合物的合成是通过掺入2孔中的卤素分子的定量转化实现的，这一点得到了单晶X射线衍射和其他结构表征的证实。嵌入的卤素间分子通过与2的多孔骨架的内部基团的相互作用而稳定，并在极性溶剂中释放并用于高选择性有机醇的碘环化。这项工作不仅为纯卤间化合物的合成打开了新的大门，而且展示了MOF晶体容器在实现经典但重要的无机和有机反应中的强大应用。