臺灣博碩士論文加值系統

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

中文摘要........................................................................................i
英文摘要.......................................................................................ii
誌謝..............................................................................................iii
目錄..............................................................................................iv
圖目錄..........................................................................................vi
表目錄..........................................................................................ix
ㄧ、緒論.......................................................................................1
1-1 前言........................................................................................1
1-2 配位超分子與自組裝............................................................2
1-3 具奈米孔洞的動態結構（動態骨架與晶體轉換）............5
1-4 具奈米孔洞的結構之離子交換..........................................10
二、實驗設計概念與合成策略.................................................13
2-1 金屬-有機配位聚合物的設計概念.....................................13
2-2 金屬與有機配子的選擇......................................................14
三、實驗部份..............................................................................17
3-1 儀器與藥品...........................................................................17
3-2 合成步驟...............................................................................18
3-2-1 K4[C10H2O8]（K4btec）之製備...................................18
3-2-2 {K2[Co3(btec)2(H2O)4]•6H2O}n (1•6H2O) 的合成.....18
3-2-3 {K2[Ni3(btec)2(H2O)4]•4H2O}n (2•4H2O) 的合成.....19
3-2-4 {Cs2[Co3(btec)2(H2O)4]•3H2O}n (3•3H2O) 的合成....19
3-2-5 {Cs2[Ni3(btec)2(H2O)4]•3H2O}n (4•3H2O) 的合成....19
3-2-6 化合物1•6H2O與氯化鉀的反應.....................................20
3-2-7 化合物2•4H2O與氯化鉀的反應.....................................20
3-2-8 化合物3•3H2O與氯化鉀的反應.....................................20
3-2-9 化合物4•3H2O與氯化鉀的反應.....................................21
3-2-10 化合物1•6H2O與氯化銫的反應.....................................21
3-2-11 化合物2•4H2O與氯化銫的反應.....................................21
3-2-12 化合物3•3H2O與氯化銫的反應.....................................22
3-2-13 化合物4•3H2O與氯化銫的反應.....................................22
3-2-14 化合物6•2H2O與氯化鉀的反應.....................................22
3-2-15 化合物9•7H2O與氯化鉀的反應.....................................23
3-2-16 化合物9•7H2O與氯化銫的反應.....................................23
3-2-17 化合物1•6H2O與氯化鋰的反應.....................................24
3-2-18 化合物2•4H2O與氯化鋰的反應.....................................24
3-2-19 化合物1•6H2O與氯化鈉的反應.....................................24
3-2-20 化合物2•4H2O與氯化鈉的反應.....................................25
3-2-21 化合物3•3H2O與氯化鈉的反應.....................................25
3-2-22 化合物4•3H2O與氯化鈉的反應.....................................25
四、實驗結果與討論....................................................................28
4-1 可溶性金屬－有機配位聚合物之合成.................................28
4-1-1 結構分析與比較...................................................................29
4-1-2 與文獻中的三核金屬簇比較...............................................37
4-2 可溶性金屬-有機化合物的重組............................................39
4-2-1 與KCl反應的結果.............................................................40
1. {K2[Ni3(btec)2(H2O)4]∙8H2O}n (5•8H2O)的結構描述.........42
2. 小總結......................................................................................42
4-2-2 與CsCl反應的結果............................................................43
第一部份、化合物1～4與CsCl反應.......................................43
1. 結構分析..................................................................................44
2. 化合物3、4於CsCl中生成之晶體的鑑定分析..................48
第二部份、化合物6與KCl反應...............................................50
1. 化合物9溶於KCl .................................................................54
2. 化合物9溶於CsCl.................................................................58
3. 小總結......................................................................................60
4-2-3 與LiCl反應的結果............................................................61
1. 化合物1與LiCl反應.............................................................62
2. 化合物2與LiCl反應.............................................................66
4-2-4 與NaCl反應的結果...........................................................69
1. 結構分析..................................................................................70
2. 化合物3、4於NaCl中的鑑定分析 .....................................74
3. 與文獻比較..............................................................................76
4-2-5 討論......................................................................................79
4-3 可溶性金屬－有機化合物的熱穩定性............................... 81
4-3-1 三核金屬簇化合物..............................................................81
4-3-2 化合物6•2H2O～13•3H2O ...............................................85
五、結論.......................................................................................87
參考文獻.......................................................................................88
附錄...............................................................................................91

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