| 摘要: | 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 |
