臺灣博碩士論文加值系統

本篇論文研究主題為利用室溫自組裝的方式，合成具有超分子結構的金屬錯合物。利用紅外線光譜儀 (IR)、元素分析儀 (EA)、熱重分析儀 (TGA)、X光單晶與粉末繞射儀來鑑定結構與量測性質。本實驗所使用的有機配基包括： L-2-amino-3-(1H-imidazol-4-yl)propanic acid (L-histidine)，以及含氮的配基4,4’-bipyridine (bipy)、5,5’-bipyrimidine (bpym)，成功的合成出三個系列的金屬錯化物：
(一)[M(L-his)2]H2O
[Zn(L-his)2]H2O (1)
[Ni(L-his)2]H2O (2)
(二){[Cd(bipy)(L-his)(H2O)]guest}n
{[Cd(bipy)(L-his)(H2O)](ClO4)}n (3)
{[Cd(bipy)(L-his)(H2O)](NO3)H2O}n (4)
(三){[Cd(bpym)0.5(L-his)(H2O)]guest}n
{[Cd(bpym)0.5(L-his)(H2O)](NO3)C2H5OH }n (5)
{[Cd(bpym)0.5(L-his)(H2O)](ClO4)H2O}n (6)
在第一系列的化合物中，化合物 1 中鋅金屬離子與兩個L-histidine分子以chelating的方式鍵結，形成tetrahedral的單體結構，單體間藉氫鍵作用力的維繫，堆疊成類似鑽石結構的三維超分子骨架；化合物 2 中鎳金屬離子和兩個L-histidine分子以tridentate的方式鍵結，形成octahedral的單體結構，在此化合物中，單體結構間除了藉由氫鍵作用力的連接外，尚有兩組三明治型的  堆積作用力，使此單體結構展現了高的熱穩定性。本系列主要是探討使用不同的金屬離子，藉由金屬的配位數不同，形成不同的幾何結構，並且發現由於單體與單體間的多組弱作用力，使化合物展現高的熱穩定性。
在第二系列的化合物中，L-histidine以bis-chelating 的方式架橋連接金屬離子形成一維鏈狀，再藉由4,4’-bipyridine互相連接，進而形成二維層狀結構。本系列的化合物對水分子均有可逆的循環吸脫附性質。在化合物4中，更發現了配位水分子的化學吸附及客體水分子的物理吸附可以清楚的被分辨。
在第三系列的化合物5及6中，鎘金屬離子和chelating/tridentate的L-histidine鍵結，形成一維的鏈狀結構，再以5,5’-bipyrimidine 連接一維長鏈，若bpym為cis form，形成二維化合物5；若bpym為trans form，則生成三維化合物6。本反應利用pyrimidine有較多的配位點及其分子結構的可扭轉性，創造結構多樣的配位聚合物。
本論文中，將詳細的介紹實驗合成方法、結構組成，利用熱重分析儀來研究其熱穩定性及水分子的循環吸脫附性質，並且藉由in-situ powder X-ray粉末繞射儀來觀察金屬錯合物在不同溫度下的結構變化。
關鍵字：掌性金屬錯合物、L-組胺酸、自組裝。

The goal of this study was to develop a self-assembly synthetic strategy for the preparation of metal–organic coordination polymers using L-2-amino-3-(1H-imidazol-4-yl)propanic acid (L-histidine), 4,4’-bipyridine (bipy) and 5,5’-bipyrimidine (bpym) in combination with different transition metal ions. The solid state structures of the products were characterized by FT-IR spectroscopy, elemental analysis, thermogravimetric analysis and single-crystal X-ray diffraction methodology.
The reaction of L-histidine with Zn(II) or Ni(II) ions leads to the formation of neutral monomeric compounds, [M(L-his)2]H2O (M = Zn (1), Ni (2)). In 1, the Zn(II) centers are coordinated by two N atoms of two different imidazoles and two N atoms of the NH2 groups of two L-histidine ligands to form a tetrahedral geometry. In 2, the nickel(II) centers are coordinated to two L-histidine ligands in a tridentate fashion through N, NH2 and O to furnish an octahedral geometry.
In another reaction, when Cd(II) ion is allowed to react with 4,4’-bipyridine and L-histidine, in the present of perchlorate (ClO4 ) or nitrate (NO3 ), the coordination polymers {[Cd(bipy)(L-his)(H2O)](ClO4)}n (3), {[Cd(bipy)(L-his)(H2O)](NO3)H2O}n (4), respectively, are formed. The molecular structures of 3 and 4 reveal that the L-histidine acts as a bridging ligand, adopting a bis-chelating coordination mode through the N atom of the NH2 group and four O atoms of carboxylates to form a 1-D chain. The 4,4’-bipyridine ligands are then connected with each chain to afford a 2-D layered structure. In these series, the de-/ad-sorption behavior of coordinated water molecules and guest water molecules are supported by TGA technology. The results show that the process is reversible when the system is exposed to water vapor. In particular, the chemical and physical adsorption behavior of 4 can be clearly differentiated from the TGA patterns.
When Cd(NO3)2 or Cd(ClO4)2 is reacted with 5,5’-bipyrimidine and L-histidine, the coordination polymers {[Cd(bpym)0.5(L-his)(H2O)](NO3)C2H5OH}n (5) and {[Cd(bpym)0.5(L-his)(H2O)](ClO4)H2O}n (6), respectively, are formed. In 5 and 6, the Cd(II) centers are coordinated with L-histidine ligands in a tetradentate coordination mode via the N atom of imidazole, the N atom of an NH2 group and two carboxylate O atoms to form a 1-D chain. In addition, 5,5’-bipyrimidine is connected to each chain of 5 and 6 via cis- and trans form, respectively, to form a 2-D layer and a 3-D structure.
Key word：chiral, L-histidine, metal-organic framework, self-assembly.

第一章 緒論 1
1-1前言 1
1-2 配基簡介 8
1-2-1 L-2-Amino-3-(1H-imidazol-4-yl)propanic acid (L-Histidine) 8
1-2-2 4,4’-Bipyridine (bipy) 11
1-2-3 5,5’-Bipyrimidine (bpym) 11
1-3 研究方法 12
1-3-1 實驗合成 12
1-3-2 試藥與儀器 13
1-3-2-1 試藥 13
1-3-2-1.1 溶劑 13
1-3-2-1.2 5,5’-Bipyrimidine 之合成及鑑定 14
1-3-2-2. 儀器 16
1-3-3 熱重分析 16
1-4 研究方向 17
第二章 18
2-1 實驗合成步驟 18
2-2 [Zn(L-his)2]H2O (1) 19
2-2-1 [Zn(L-his)2]H2O (1) 的合成 19
2-2-2 [Zn(L-his)2]H2O (1) 晶體數據之收集與處理 20
2-2-3 [Zn(L-his)2]H2O (1) 結構敘述 22
2-2-4 [Zn(L-his)2]H2O (1) 之熱重分析 25
2-3 [Ni(L-his)2]H2O (2) 26
2-3-1 [Ni(L-his)2]H2O (2) 的合成 26
2-3-2 [Ni(L-his)2]H2O (2) 晶體數據之收集與處理 27
2-3-3 [Ni(L-his)2]H2O (2) 結構敘述 29
2-3-4 [Ni(L-his)2]H2O (2) 性質量測 33
2-3-4.1化合物2之熱重分析與變溫粉末繞射量測 33
2-3-4.2化合物2之水分子之循環吸脫附實驗 35
2-4 實驗結果討論 37
第三章 39
3-1 實驗合成步驟 39
3-2 {[Cd(bipy)(L-his)(H2O)](ClO4)}n (3) 40
3-2-1 {[Cd(bipy)(L-his)(H2O)](ClO4)}n (3) 的合成 40
3-2-2 {[Cd(bipy)(L-his)(H2O)](ClO4)}n (3) 晶體數據之收集與處理 41
3-2-3 {[Cd(bipy)(L-his)(H2O)](ClO4)}n (3) 結構敘述 44
3-2-4 {[Cd(bipy)(L-his)(H2O)](ClO4)}n (3) 性值量測 47
3-2-4.1化合物3之熱重分析與粉末繞射量測 47
3-2-4.2化合物3之水分子循環吸脫附實驗 49
3-3 {[Cd(bipy)(L-his)(H2O)](NO3)H2O}n (4) 51
3-3-1 {[Cd(bipy)(L-his)(H2O)](NO3)H2O}n (4) 的合成 51
3-3-2 {[Cd(bipy)(L-his)(H2O)](NO3)H2O}n (4) 晶體數據之收集與處理 52
3-3-3 {[Cd(bipy)(L-his)(H2O)](NO3)H2O}n (4) 結構敘述 54
3-3-4 {[Cd(bipy)(L-his)(H2O)](NO3)H2O}n (4) 性值量測 57
3-3-4.1化合物4之熱重分析與變溫粉末繞射量測 57
3-3-4.2化合物4之水分子之循環吸脫附實驗 60
3-4 實驗結果與討論 64
第四章 66
4-1 實驗合成步驟 66
4-2 {[Cd(bpym)0.5(L-his)(H2O)](NO3)C2H5OH}n (5) 67
4-2-1 化合物5的合成 67
4-2-2 化合物5晶體數據之收集與處理 68
4-2-3 {[Cd(bpym)0.5(L-his)(H2O)](NO3)C2H5OH}n (5) 結構敘述 70
4-2-4 化合物5之熱重分析 73
4-3 {[Cd(bpym)0.5(L-his)(H2O)](ClO4)H2O}n (6) 75
4-3-1 化合物6的合成 75
4-3-2 化合物6晶體數據之收集與處理 76
4-3-3 {[Cd(bpym)0.5(L-his)(H2O)](ClO4)H2O}n (6) 結構敘述 78
4-3-4 {[Cd(bpym)0.5(L-his)(H2O)](ClO4)H2O}n (6) 之熱重分析 81
4-4 實驗結果與討論 83
第五章 總結 84
參考文獻 87

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