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研究生: 許良平
Liang-Ping Shu
論文名稱: 鎳、鈷、銅金屬離子與吡啶-羧酸混配子
Design of Inorganic-Organic Hybrid Materials Based on Pyridine and Carboxylate Mixed Ligands
指導教授: 李光華
Kwang-Hwa Lii
呂光烈
Kuang-Lieh Lu
口試委員:
學位類別: 碩士
Master
系所名稱: 理學院 - 化學學系
Department of Chemistry
畢業學年度: 94
語文別: 中文
論文頁數: 180
中文關鍵詞: 超分子配位聚合物
外文關鍵詞: supramolecule, coordination polymer
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  • 中文摘要
    本論文研究重點在於探討混配子(吡啶和羧酸衍生物)和金屬陽離子(Ni2+、Co2+、Cu2+) 經水熱反應得到一系列配位聚合物之結構與性質。
    本文針對有機配子的組合型式,區分為兩種類型。第一類型是以2,6-naphthalenedicarboxylic acid (2,6-H2ndc)和 4,4’-bipyridine (4,4’-bpy) 或 trans-1,2-bis(4-pyridyl)ethylene (bpe) 為混配子,分別與鎳、鈷金屬的鹽類在水熱條件下反應,分別得到各化合物[{Ni(2,6-ndc)(4,4’-bpy)1/2}]n (1)、 [{Co(2,6-ndc)(4,4’-bpy)1/2}]n (2)、 [{Ni (2,6-ndc)(bpe)H2O}]n (3)、 [{Co2(2,6-ndc)2(bpe)}3.H2O]n (4)。單晶X-ray繞射鑑定分析顯示1、2為等結構化合物,具有特殊的互穿結構。第二類型則是以benzene-1,3,5-tricarboxylic acid (1,3,5-H3btc)和4,4’-dipyridylpiperazine (2N-DPyP) 為混配子,與銅、鎳金屬的鹽類反應,分別得到化合物[{Cu(1,3,5-btc)} (2N-DPyPH2)1/2‧2H2O]n (5)、 [{Ni(1,3,5-btc)(2N-DPyPH)(2N-DPyP)1/2(H2O)}‧H2O]n (6)、 [{Ni3(1,3,5-btc)2 (2N-DPyP)3(H2O)2}‧2H2O]n (7)。而化合物6、7的產率可由溶液pH值和金屬配子比例而調控。


    Abstract
    The self-assembly of Ni2+, Co2+ or Cu2+ ions with pyridine and carboxylate mixed ligands under hydrothermal conditions afforded a series of coordination polymers. The solid state structures of the products were characterized by single-crystal X-ray diffraction analyses.
    Treatment Ni2+ or Co2+ ions with mixed ligands of 2,6-naphthalenedicarboxylic acid (2,6-H2ndc) and 4,4’-bipyridine (4,4’-bpy) or trans-1,2-bis(4-prydyl)-ethylene (bpe) under hydrothermal conditions gave compounds [{Ni(2,6-ndc)(4,4’-bpy)1/2}]n (1)、 [{Co(2,6-ndc)(4,4’-bpy)1/2}]n (2)、 [{Ni (2,6-ndc)(bpe)H2O}]n (3) and [{Co2(2,6-ndc)2(bpe)}3.H2O]n (4), respectively. Single-crystal X-ray diffraction analyses reveals that compound 1 and 2 are isostructures with interpenetrated architectures. Reaction of Ni2+ ion with benzene-1,3,5-tricarboxylic acid (1,3,5-H3btc) and 4,4’-dipyridylpiperazine (2N-DPyP) via hydrothermal method produced compounds [{Ni(1,3,5btc)(2N-DPyPH)(2N-DPyP)1/2(H2O)}‧H2O]n (6) and [{Ni3(1,3,5-btc)2(2N-DPyP)3(H2O)2}‧2H2O]n (7). Under similar reactions, Cu2+ reacted with 1,3,5-H3btc and 2N-DPyP to form [{Cu(1,3,5-btc)}(2N-DPyPH2)1/2‧2H2O]n (5). However, the yield of compounds 6 and 7 could be tuned by changing the pH value and the metal to ligand ratio in the solution.

    目次 頁次 中文摘要 I 英文摘要 II 致謝 III 圖目錄 iii 表目錄 vii 第一章 序論 1 1.1 超分子化學 (supramolecular) 1 1.2 晶體工程 (crystal engineering) 10 1.2.1 自組裝 (self-assembly) 10 1.2.2 單體超分子和配位聚合物 (discrete supramolecule and coordination polymer) 12 1.3水熱反應 (hydrothermal reaction) 17 1.4實驗設計概念 21 1.4.1 研究動機 21 1.4.2 金屬與有機配位子之選擇 23 第二章 實驗部份 25 2.1 儀器 25 2.2 藥品 27 2.3 有機配子 4,4’-dipyridylpiperazine (2N-DPyP) 之合成 28 2.4 金屬和混有機配子配位聚合物之合成 30 第三章 結果與討論 51 第四章 結論 95 參考文獻 96 附錄: 原子位置和熱參數及鍵長與鍵角表 99

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