A Significant Two-Dimensional Structural Transformation in a Coordination Polymer that Changes Its Electronic and Protonic Behavior |
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Authors: | Yao Jing Prof Yukihiro Yoshida Prof Tokutaro Komatsu Prof Hiroshi Kitagawa |
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Institution: | 1. Division of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto, 606-8502 Japan;2. School of Medicine, Nihon University, 30-1 Oyaguchi-Kamicho, Itabashi-ku, Tokyo, 173-8610 Japan |
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Abstract: | A 2D-to-2D (2D: two-dimensional) structural transformation accompanying significant bond rearrangement and coordination environment change is demonstrated in a coordination polymer (CP) comprised of copper(II) ions and terephthalate (BDC2−) ligands for the first time. When immersed in water, a free-standing membrane of 2D Cu(BDC)(DMF) ( Cu-1 ; DMF: N,N-dimethylformamide) transforms into 2D Cu(BDC)(H2O)2 ( Cu-2 ) while maintaining its highly oriented layered structure. In the 2D sheet, paddlewheel-type CuII dimers coordinated with four bidentate BDC ligands in a square-planar array in Cu-1 were released to form uniform aqua-bridged CuII chains, which are cross-linked with each other by unidentate BDC ligands, in Cu-2 . The present facile approach to implement the 2D-to-2D transformation accompanied by bond rearrangement, which is characteristic of CPs, leads to a marked increase in in-plane magnetic susceptibility and proton conductivity. In situ experiments in support of theoretical calculations unveiled the energy diagram that governs the unique structural transformation. |
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Keywords: | 2D-to-2D Transformation Coordination Polymer Magnetism Proton Conductivity |
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