Self-Assembly of Four Coordination Polymers in Three-Dimensional Entangled Architecture Showing Reversible Dynamic Solid-State Structural Transformation and Color-Changing Behavior upon Thermal Dehydr

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• 作者：Szu-Yu Ke ; Ya-Fan Chang ; Hsin-Yu Wang ; Ching-Chun Yang ; Cheng-Wei Ni ; Gu-Ying Lin ; Tzu-Ting Chen ; Mei-Lin Ho ; Gene-Hsiang Lee ; Yu-Chun Chuang ; Chih-Chieh Wang
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：August 6, 2014
• 年：2014
• 卷：14
• 期：8
• 页码：4011-4018
• 全文大小：496K
• ISSN：1528-7505

文摘

A unique three-dimensional (3D) supramolecular compound, [Co(dpe)(BTC)(H₂O)][Co(dpe)(BTC)(H₂O)₃][Co(dpe)(HBTC)(H₂O)][Co(dpe)₂(H₂O)_3.5(EtOH)_0.5]路1.5H₂O (1; dpe = 1,2-bis(4-pyridyl)ethane and H₃BTC = benzenetricarboxylic acid), has been synthesized and structurally characterized by the single-crystal X-ray diffraction method. Compound 1 consists of four coordination polymers (CPs), two are two-dimensional (2D) layered metal鈥搊rganic frameworks (MOFs) with (4,4) topology of [Co(dpe)(BTC)(H₂O)]^{鈭?/sup> and [Co(dpe)(HBTC)(H₂O)], whereas the other two are one-dimensional (1D) polymeric chains of [Co(dpe)(BTC)(H₂O)₃]鈭?/sup> and [Co(dpe)(H₂O)_3.5(EtOH)_0.5]2+. The 3D supramolecular architecture of 1 is constructed via the penetration of interdigitated double-layered 2D rectangular-grid frameworks by two 1D coordination polymeric chains and entangled tightly by the subtle combination of intermolecular hydrogen bonding and 蟺鈥撓€ interactions among the four CPs. Controlled heating of the as-synthesized crystal 1 at 160 掳C produces a desolvated 1 and accompanying color-changing behavior from pink to deep-blue, and the deep-blue desolvated 1 regenerates the pink rehydrated crystal with the chemical formula of [Co(dpe)(BTC)(H₂O)][Co(dpe)(BTC)(H₂O)₃][Co(dpe)(HBTC)(H₂O)][Co(dpe)₂(H₂O)₄]路3H₂O (2) upon exposure to water vapor. The structural determination of 2 shows almost the same structural characteristics as that of 1 with the only difference being the replacement of disordered coordinated solvent (half H₂O and half EtOH molecules) by H₂O and the numbers of solvated water molecules. The cyclic thermogravimetric analysis and powder X-ray diffraction measurements of desolvated 1 demonstrate a reversible rehydration/dehydration property, which is associated with solid-state structural transformation and thermally induced UV鈥搗is absorption properties.}