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研究生:葉臻
研究生(外文):Zhen Yeh
論文名稱:含1,4-二(磷酸亞甲基)-2,3,5,6-四甲基苯配子配位聚合物之自組裝
論文名稱(外文):Self-assembly, Structures, and Properties of1,4-Bis(methylene phosphonic acid)-2,3,5,6- tetramethylbenzene Containing Coordination Polymers
指導教授:呂光烈曾添文
口試委員:楊振宜楊重光陳生明
口試日期:2013-06-21
學位類別:碩士
校院名稱:國立臺北科技大學
系所名稱:化學工程研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2013
畢業學年度:101
語文別:中文
論文頁數:109
中文關鍵詞:配位聚合物磷酸基配位分子自組裝
外文關鍵詞:coordination polymerphosphonate ligandself-assembly
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本文研究為二磷酸基的有機配子1,4-bis(methylene phosphonic acid) 2,3,5,6-tetramethylbenzene (H4bmpb)與過渡金屬離子 (CoII、MnII)和鹼土族離子(BaII),在調控的酸鹼及溫度環境下,進行自組裝合成,製備有機-無機金屬之配位聚合物。

以H4bmpb與過渡金屬離子(MnII、CoII)與鹼土族離子(BaII)利用室溫反應方式,在調控pH值下,得到兩個相類似結構的一維鍊狀配位聚合物 {[Co(H2bmpb)(H2O)4]‧2H2O}n (1)、{[Mn(H2bmpb)(H2O)4]‧2H2O}n (2),及得到一個共結晶複合物{[Ba2(H2O)12‧(bmpb)]‧4H2O} (3),一併探討其結構特性與物性分析。利用H4bmpb與過渡金屬離子(CoII)分別與4,4''-bipyridine配子及2,2''-bipyridine配子進行自組裝合成。利用室溫下反應,得到二維平面結構{[Co(H2bmpb)(4,4-bpy)(H2O)2]‧2H2O}n (4),及在恆溫60℃得到一維鍊狀配位聚合物 {[Co(H2bmpb)(2,2-bpy)(H2O)2]‧2H2O}n (5),最後一併探討其結構特性與物性分析。


In this thesis, a bis-phosphonate acid ligand 1,4-bis(methylene phosphonic acid) 2,3,5,6-tetramethylbenzene (H4bmpb) was reacted with transition-metal ions (MnII, CoII), and alkaline earth ions (BaII), at different temperatures and at different pH values, resulting in the formation of five coordination polymers 1-5.
When the H4bmpb ligand was reacted with transition-metal ions (MnII, CoII), three coordination polymers were produced. Compounds 1 and 2 were prepared under different reaction conditions at different pH values. Compounds 1 and 2 were characterized by single-crystal X-ray diffraction analyses. The compounds are isostructures and adopt a 1D chain topology. Compound 3 was obtained as a co-crystal. The thermal stability and physical properties of the complexes were also examined.
Compounds 4 and 5 were produced by the reaction of H4bmpb with a transition-metal ion (CoII) in the presence of 4,4''-bipyridine or 2,2''-bipyridine. Compound 4 is a 2D coordination polymer. The 2D layers are further stacked into a 3D MOF. However, when the temperature was increased to 60 °C, compound 5 was produced. This compound is a 1D chain and the chains are further linked into a 2D sheet. The structures, thermal stabilities and physical properties of products 1-5 are discussed in this thesis.


目錄
摘要 I
ABSTRACT II
致謝 IV
表目錄 VII
圖目錄 VIII
第一章 緒論 1
1.1. 前言 1
1.2. 配位聚合物 (COORDINATION POLYMER) 2
1.3. 實驗動機 21
第二章 實驗部分 25
2.1. 儀器與藥品 25
2.2. 有機配子與化合物合成 27
第三章 結果與討論 31
3.1. 化合物{[M(H2BMPB)(H2O)4]‧2H2O}N [M = CO (1), MN (2) ] 的合成與結構描述及其性質分析: 31
3.2. 化合物{[BA2(H2O)12‧(BMPB)]‧4H2O} (3)的合成與結構描述及其性質分析: 40
3.3. 化合物{[CO(H4BMPB)(4,4’-BPY)(H2O)2]‧2H2O}N (4)的合成與結構描述及其性質分析 44
3.4. 化合物{[CO(H4BMPB)(2,2’-BPY)(H2O)2]‧2H2O}N (5)的合成與結構描述及其性質分析 53
第四章 結論 60
參考資料 61
附錄 64

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