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    Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/6450

    Title: 可溶性含四羧酸-鈷、鎳配位聚合物之自組裝合成與重組;Soluble Metal-Organic Frameworks: Dissolution/Reassembly towards the Structural Rearrangement of Porous Cobalt(II)- and Nickel(II)–Carboxylate Coordination Polymers
    Authors: 丁妙慈;Miao-Tzu Ding
    Contributors: 化學研究所
    Keywords: 拆解/重組;結構轉換;自組裝;超分子;structural transformation;dissolution/reassembly;self-assembly;supermolecular
    Date: 2008-04-30
    Issue Date: 2009-09-22 10:19:43 (UTC+8)
    Publisher: 國立中央大學圖書館
    Abstract: 本論文研究重點在於利用自組裝的方式,將四羧酸benzene-1,2,4,5-tetracarboxylic acid (H4btec)與鈷、鎳金屬離子利用水熱合成法製備具有孔洞結構的金屬-有機配位聚合物。 利用H4btec與鈷、鎳金屬離子經由自組裝的方式合成四個三維孔洞結構{K2[Co3(btec)2(H2O)4]∙6H2O}n (1•6H2O)、{K2[Ni3(btec)2(H2O)4]•4H2O}n (2•4H2O)、{Cs2[Co3(btec)2(H2O)4]•3H2O}n (3•3H2O)與{Cs2[Ni3(btec)2(H2O)4]•3H2O}n (4•3H2O)。此四個化合物皆由具4個連接樞紐之btec4-為節點與具8個連接樞紐之三核金屬簇M3(O2C)8(H2O)4為另一節點構成(4,8)-連接網狀架構,均具有ㄧ維親水通道之三維金屬-有機孔洞配位聚合物,鹼金屬陽離子(KI或CsI)與客分子水都充斥在孔道中。 上述所生成之可溶性三維金屬-有機孔洞配位聚合物均可溶於鹼金屬氯化鹽(LiCl、NaCl、KCl、CsCl)水溶液中。藉由拆解-重組的方式,可溶性金屬-有機配位聚合物(1?4)會溶解而重新組合轉變為新的化合物(5?13)。其結構藉由單晶及粉末繞射技術鑑定,其固態結構之變化頗為豐富有趣,其中化合物1、6、9,之間有結構轉換性,這更是本篇論文最有趣的地方。 The goal of this study was to develop a self-assembly synthetic strategy for the preparation of metal–organic coordination polymers using benzene-1,2,4,5-tetracarboxylic acid (H4btec) and transition-metal ions (CoII, NiII). Four three-dimensional, soluble, porous metal–organic coordination networks {K2[Co3(btec)2(H2O)4]∙6H2O}n (1•6H2O), {K2[Ni3(btec)2(H2O)4]•4H2O}n (2•4H2O), {Cs2[Co3(btec)2(H2O)4]•3H2O}n (3•3H2O), and {Cs2[Ni3(btec)2(H2O)4]•3H2O}n (4•3H2O) with near identical structural features were hydrothermally prepared. These structures adopt a (4,8)-connected net consisting of a four-connected square-planar node of a btec4- ligand and an eight-connected node of trinuclear clusters M3(O2C)8(H2O)4. These three-dimensional frameworks possess hydrophilic channels, where the alkali metal ions (KI or CsI) and free water molecules reside. Ion-exchange studies, by treating 1?4 in an aqueous solution of alkali chloride (LiCl, NaCl, CsCl and KCl), revealed that a surprisingly dissolution/reassembly process occurred, leading to the rearrangement of metal–carboxylate building blocks and the formation of new metal–carboxylate species (5?13). The structural transformations were confirmed by single-crystal and powder X-ray diffraction (PXRD) data
    Appears in Collections:[化學研究所] 博碩士論文

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