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研究生: 詹鈞傑
Chun-Chieh Chan
論文名稱: 銀離子與5,5''-聯嘧啶自組裝合成、結構與性質研究
Silver(I) ion with 5,5''-bipyrimidine self-assembly synthesized, structure and physical properties study.
指導教授: 呂光烈
Kuang-Lieh Lu
李光華
Kwang-Hwa Li
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: 91
語文別: 中文
論文頁數: 131
中文關鍵詞: 類礦石結構陰離子交換固態相轉變自組裝合成
外文關鍵詞: self-assembly synthesis, mineral-like structure, anion exchange, solid-state phase transform
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  • 中文摘要
    本篇論文旨趣在於嘗試以室溫自組裝的合成方法,製備具礦石結構排列的金屬-有機配位聚合物。同時藉著陰離子的調控,合成一系列含銀配位聚合物。由X射線單晶繞射獲得晶體結構,相關數據如下所示;化合物(1) [Ag(C8H6N4)](CF3SO3) 為透明晶體,屬Trigonal,空間群P3221,a = 10.8139(2) Å,b = 10.8139(2) Å,c = 9.7481(2) Å,α = 90 o,β = 90 o,γ = 120 o,為三維類石英結構。
    化合物(2) [Ag(C8H6N4)](PF6) 為白色半透明晶體,屬Orthorhombic,空間群Fdd2,a = 17.2360(17) Å,b = 9.1835(9) Å,c = 15.4780(16) Å,α = 90 o,β = 90 o,γ = 90 o,為三維類鑽石結構。
    化合物(3) [Ag(C8H6N4)](BF4) 為白色半透明晶體,屬Monoclinic,空間群P21/n,a = 9.8609(2) Å,b = 8.5499(2) Å,c = 13.1795(2) Å,α = 90 o,β = 104.3770(9) o,γ = 90 o,為二維黏土結構。
    化合物(4) [Ag(C8H6N4)](ClO4) 為透明晶體,屬Monoclinic,空間群P21/n,a = 9.8779(15) Å,b = 8.6504(13) Å,c = 13.223(2) Å,α = 90 o,β = 104.612(3) o,γ = 90 o,為二維黏土結構。
    化合物(5) [Ag(C8H6N4)(H2O)(NO3)] 為透明晶體,屬Monoclinic,空間群P21/n,a = 9.5531(15) Å,b = 6.6706(10) Å,c = 16.731(3) Å,α = 90 o,β = 95.501(3) o,γ = 90 o,為二維4.82結構。


    The research goal of this work is to synthesize mineral-like structure via self-assembly strategy. In order to simulate mineral structure, we have selected a suitable organic building block 5,5’-bipyrimidine. By link this organic ligand with proper metal centers, several flexable coordination polymers have been prepared and characterized. Crystal data as follow:
    Compound (1): [Ag(C8H6N4)](CF3SO3), M = 415.11, trigonal, space group P3221, a = 10.8139(2), b = 10.8139(2), c = 9.7481(2) Å, α = 90, β = 90, γ = 120 o, U = 987.22(3) Å3, Z = 3, R1 = 0.0484, wR2 = 0.0954.
    Compound (2) [Ag(C8H6N4)](PF6), M = 410.995, orthogombic, space group Fdd2, a = 17.2360(17), b = 9.1835(9), c = 15.4780(16) Å, α = 90, β = 90, γ = 90 o, U = 2449.96(42) Å3, Z = 8, R1 = 0.0242, wR2 = 0.0610.
    Compound (3) [Ag(C8H6N4)](BF4), M = 352.85, monoclinic, space group P21/n, a = 9.8609(2), b = 8.5499(2), c = 13.1795(2) Å, α = 90, β = 104.3770(9), γ = 90 o, U = 1076.36(4) Å3, Z = 4, R1 = 0.0318, wR2 = 0.0778.
    Compound (4) [Ag(C8H6N4)](ClO4), M = 365.49, monoclinic, space group P21/n, a = 9.8779(15), b = 8.6504(13), c = 13.223(2) Å, α = 90, β = 104.612(3), γ = 90 o, U = 1093.3(4) Å3, Z = 4, R1 = 0.0386, wR2 = 0.1846.
    Compound (5) [Ag(C8H6N4)(H2O)(NO3)], M = 346.06, monoclinic, space group P21/n, a = 9.5531(15), b = 6.6706(10), c = 16.731(3) Å, α = 90, β = 95.501(3), γ = 90 o, U = 1061.3 (3) Å3, Z = 4, R1 = 0.0202, wR2 = 0.0502.

    目錄 中文摘要………………………………………………………………Ⅰ 英文摘要………………………………………………………………Ⅱ 表次……………………………………………………………………Ⅴ 圖次……………………………………………………………………Ⅶ 第一章緒論 第一節、前言………………………………………………………1 第二節、金屬與有機配子配位聚合物中的作用力介紹…………3 第三節、金屬與有機配子配位聚合物分類介紹…………………9 第二章實驗設計概念 第一節、金屬中心與有機配子之選擇……………………………14 第二節、5,5’-聯嘧啶合成方式選擇………………………………17 第三章實驗 第一節、儀器與藥品………………………………………………18 第二節、5,5’-聯嘧啶之合成與鑑定………………………………21 第三節、5,5’-聯嘧啶-銀鹽配位聚合物合成………………………26 第四節、配位聚合物晶體數據與ORTEP 圖……………………29 第五節、陰離子交換實驗…………………………………………41 第四章結果與討論 第一節、三維結構與光譜分析……………………………………42 第二節、二維三配位結構與光譜分析……………………………66 第三節、二維五配位結構與光譜分析……………………………85 第五章總結 第一節、結論………………………………………………………95 第二節、未來工作建議……………………………………………97 參考文獻………………………………………………………………98 附錄 原子位置和熱參數及鍵長與鍵角表………………………………103

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