臺灣博碩士論文加值系統

中文摘要
本論文主要探討含N,N'-二-(4-吡啶)己二醯二胺配位基(H2dpya)及含雙羧酸基苯甲酸(1,4-BDC)與過渡金屬二價鋅與二價鎘之化學。利用了水熱法合成出[Zn(1,4-BDC)(H2dpya)] •(H2O)，1和[Cd(1,4-BDC)(H2dpya)] •2(H2O) ，2，以上兩種化合物均利用元素分析儀鑑定、紅外光光譜儀、熱重分析儀和螢光光譜儀分析特性，而單晶結構均以單晶 X-ray 繞射儀鑑定。
在化合物1與化合物2中，藉由配位基N,N'-二-(4-吡啶)己二醯二胺與對苯二甲酸的橋接，形成了三維扭曲的鑽石型結構，化合物1為[4+4]的貫穿模式，化合物2為9層相互貫穿模式，配位基H2dpya在化合物1中為AGA-cis的構型；在化合物2中為AAA-trans的構型，表現出配位基H2dpya具有良好的柔軟性質。

Abstract
This thesis discusses the chemistry of znic(II) and cadmium(II) complexes containing N,N'-di(4-pyridyl)adipoamide (H2dpya) and 1,4-benzenedicarboxylate (1,4-BDC). Two new coordination polymers, [Zn(1,4-BDC)(H2dpya)] •(H2O) (1) and [Cd(1,4-BDC)(H2dpya)] •2(H2O) (2), have been synthesized by hydrothermal reactions. All the complexes have been characterized by EA, IR, TGA and PL spectroscopic methods and structurally characterized by X-ray crystallography.
Complex 1 and complex 2 form the distorted diamondoid net supported by N,N'-di(4-pyridyl)adipoamide and 1,4-benzenedicarboxylate. Complex 1 is a [4+4] mode of interpenetration and complex 2 is a 9-fold interpenetrating mode. The H2dpya ligands in complex 1 adopts the AGA-cis conformation while in complex 2 the AAA-trans onformation.

目錄
中文摘要.............................................................................I
Abstract...............................................................................II
謝誌..................................................................................III
目錄..........................................................................................................IV
表目錄......................................................................................................VI
附錄表目錄……………………………………………………………..VI
圖目錄.....................................................................................................VII
第一章 總論
1-1 序論..............................................................................................1
1-2 配位基介紹..................................................................................5
1-3 研究動機......................................................................................8
第二章 實驗
2-1 實驗藥品.....................................................................................9
2-2 合成化合物……………………………………………………10
2-3 單晶繞射X-ray與晶體解析......................................................12
第三章 化合物結構討論與性質測試
3-1 化合物結構................................................................................15
3-2 TGA熱性質分析.........................................................................22
3-3 放光性質測試………………………………...……………….24
3-4 氣體吸脫附測試………………………………………………26
第四章 結論……………………………………………………………29
參考文獻………………………………………………………………..30
附錄..........................................................................................................34

表目錄
表 1 化合物1晶體資料..........................................................................13
表 2 化合物2晶體資料..........................................................................14
表 4 配位基與化合物1化合物2激發與放光波段................................24
附錄表目錄
Table 1. Atomic coordinates ( x 104) and equivalent isotropic isplacement
parameters (A2 x 103) for [Zn(1,4-BDC)(H2dpya)] •(H2O).…...35
Table 2. Bond lengths [Å] for [Zn(1,4-BDC)(H2dpya)] •(H2O)………...37
Table 3. Bond angles [°] for [Zn(1,4-BDC)(H2dpya)] •(H2O)…………..39
Table 4. Hydrogen coordinates ( x 104) and isotropic displacement
parameters (A2 x 103) for [Zn(1,4-BDC)(H2dpya)] •(H2O) .…..41
Table 5. Atomic coordinates ( x 104) and equivalent isotropic isplacement
parameters (A2 x 103) for [Cd(1,4-BDC)(H2dpya)] •2(H2O)......42
Table 6. Bond lengths [Å] for [Cd(1,4-BDC)(H2dpya)] •2(H2O).............44
Table 7. Bond angles [°] for [Cd(1,4-BDC)(H2dpya)] •2(H2O)………...46
Table 8. Anisotropic displacement parameters (A2 x 103) for [Cd(1,4-BDC)(H2dpya)] •2(H2O) ...…………………………...48
Table 9. Hydrogen coordinates ( x 104) and isotropic displacement
parameters (A2 x 103) for [Cd(1,4-BDC)(H2dpya)] •2(H2O)…..50

圖目錄
圖 1 配位化合物自我組裝示意圖..........................................................2
圖 2 配位基分類：(A)無機配位基；(B)中性配位基
(C)陰離子型位基；(D)陽離子型配位基.......................................3
圖 3 配位高分子的結構示意圖..............................................................4
圖 4 具有雙吡啶環的架橋配位基……………………………………..5
圖 6 雙吡啶環配位基所合成多樣化的結構..........................................7
圖 7 (a) 化合物1非對稱單元結構圖 (b) 化合物1中心金屬構型…..15
圖 8 化合物1藉由配位基橋接形成扭曲鑽石型結構………………..17
圖 9 (a) 化合物1單層4個結構相互貫穿 (b) 化合物1形成[4+4]相互
貫穿結構…………………………………………………………17
圖 10 化合物2非對稱單元結構圖……………………………………18
圖 11 化合物2藉由配位基橋接形成扭曲鑽石型結構………………19
圖 12 化合物2形成9層相互貫穿結構………………………………..19
圖 13 化合物1與化合物2所形成的空間大小示意圖..........................20
圖 14 化合物1熱重損失圖……………………………………………22
圖 15 化合物2熱重損失圖....................................................................23
圖 16 配位基與化合物的放光光譜…………………………………..25
圖 17 (a) 化合物2氮氣吸脫附圖 (b) 化合物2氫氣吸脫附圖……...27
圖 18 化合物2氫氣吸脫附圖................................................................28

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