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A Step‐by‐Step Assembly of a 3D Coordination Polymer in the Solid‐State by Desolvation and [2+2] Cycloaddition Reactions
Authors:Dr. Raghavender Medishetty  Rika Tandiana  Dr. Jien Wu  Zhaozhi Bai  Dr. Yonghua Du  Prof. Jagadese J. Vittal
Affiliation:1. Department of Chemistry, National University of Singapore, Singapore 117543, Fax: (+65)?6779‐1691;2. Institute of Chemical and Engineering Science, Agency for Science & Technology and Research, 1 Pesek Road, Jurong Island, Singapore 627833, Fax: (+65)?6773‐6734
Abstract:Two solid‐state structural transformations that occur in a stepwise and a controlled manner are described. A combination of desolvation and cycloaddition reactions has been employed to synthesise a 3D coordination polymer (CP) from 1D CP [Cd(bdc)(4‐spy)2(H2O)]?2 H2O?2 DMF (bdc=1,4‐benzenedicarboxylate, 4‐spy=4‐styrylpyridine) presumably via a 2D layered structure, [Cd2(bdc)2(4‐spy)4]. In the absence of single crystals to follow the course of the photocycloaddition reaction, thermogravimetry, XAFS and NOESY NMR experiments were used to propose the formation of layered and pillared layered structures. Further, the present strategy enables us to synthesise new multidimensional architectures that are otherwise inaccessible by the self‐assembly process.
Keywords:cycloaddition  coordination polymers  desolvation  mechanochemical synthesis  metal–  organic frameworks  solid‐state reactions
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