臺灣博碩士論文加值系統

本論文探討Mn(II)、Co(II)、Ni(II) 這三種過渡金屬，分別與丙二酸衍生物：二甲基丙二酸 (H2-Me2mal) 及二乙基丙二酸 (H2-Et2mal)，搭配4,4′-聯吡啶 (bpy) 和1,2-二(4-吡啶基)乙烯 (dpe) 用水浴合成法及水熱合成法製備出{[Mn(Me2mal)(bpy)0.5(H2O)]}n (1)、{[Co(Me2mal)(bpy)0.5(H2O)]}n (2)、{[Ni(Me2mal)(bpy)0.5(H2O)]}n (3)、{[Mn(H-Et2mal)2(bpy)(H2O)2]}n (4)、{[Co2(Et2mal)2(bpy)2(H2O)2]•2H2O•2DMF}n (5)、{[Ni2(Et2mal)2(bpy)2(H2O)2]•2H2O•2DMF}n (6)、{[Co(Me2mal)(dpe)0.5(H2O)]}n (7)及{[Co2(Me2mal)2(dpe)]}n (8)八個配位聚合物，探討其固態結構與磁性之關係。
化合物 (1)-(3) 為三維結構，除中心金屬不同之外，晶體結構與羧酸配位子 (Me2mal) 連接模式皆一致。化合物 (1)-(3) 的磁性分析發現在相同電子傳導路徑下，對於擁有不同自旋數的中心金屬，所形成之相異磁行為，當自旋數越高的時候，越傾向反鐵磁性行為。
化合物 (4)-(6) 為三維結構，除了化合物 (4) 的配位環境不同外，化合物 (5) 與 (6) 的晶體結構與羧酸配位子 (Et2mal) 連接模式一致。化合物 (5) 與(6) 的磁性分析發現在相同電子傳導路徑下，對於擁有不同自旋數的中心金屬，會發生不一樣的磁性行為。化合物 (5) 與 (6) 其結果也如同化合物 (2) 與 (3)，當自旋數越高的時候，越傾向反鐵磁性行為。
其丙二酸衍生物在化合物 (1)-(6) 裡，磁性的電子傳遞路徑皆為syn-anti的連接模式，取代基的不同明顯地影響整體結構的呈現，從化合物 (1)-(3) 為2維的syn-anti連接模式到化合物 (5)-(6) 的1維syn-anti連接模式。
化合物 (7) 與(8) 在不同溫度下合成，化合物 (7) 之固態結構可在水熱條件下，進行晶體重組 (crystal reassembly) 形成化合物 (8a)，當結構改變時，電子傳導路徑由原來syn-anti變成由兩個羧酸配位子 (Me2mal) 以syn-syn的方式連接，當Co與Co距離變近時，在低溫下會展現鐵磁性行為。

This research is focus on the synthesis of transition metal coordination polymers (Mn, Co, Ni) based on the malonic acid derivatives Dimethylmalonic acid (H2-Me2mal), and Diethylmalonic acid (H2-Et2mal), and 4,4′-Bipyridine (bpy) and 1,2-Di(4-pyridyl)ethylene (dpe). The compounds {[Mn(Me2mal)(bpy)0.5(H2O)]}n (1), {[Co(Me2mal)(bpy)0.5(H2O)]}n (2), {[Ni(Me2mal)(bpy)0.5(H2O)]}n (3), {[Mn(H-Et2mal)2(bpy)(H2O)2]}n (4), {[Co2(Et2mal)2(bpy)2(H2O)2]•2H2O•2DMF}n (5), {[Ni2(Et2mal)2(bpy)2(H2O)2]•2H2O•2DMF}n (6), {[Co(Me2mal)(dpe)0.5(H2O)]}n (7), and {[Co2(Me2mal)2(dpe)]}n (8), have been synthesized from the waterbath and hydrothermal methods. The crystal structures and magnetic properties have been studied.
Compounds (1)-(3) show 3D structure, and are isostructure, in which metal ions linked through 2D syn-anti carboxylate bridges. Magnetic analysis show that synanti bridging carboxylate mediate antiferromagnetic interaction within compounds (1)-(2), in contrast, mediate ferromagnetic interaction in compound (3).

Compounds (5) and (6) show 3D structure, and are isostructure, in which metal ions linked through 1D syn-anti carboxylate bridges. Magnetic analysis show that syn-anti bridging carboxylate mediate antiferromagnetic interaction within compounds (5), in contrast, mediate ferromagnetic interaction in compound (6).
In compound (1)-(6), malonic acid derivatives are same syn-anti bridging mode to mediate magnetic behaviors, compound structures are different by substituent effect. In compound (1)-(3) are 2D syn-anti briding mode, compound (5)-(6) are 1D syn-anti briding mode.
Compounds (7) and (8) are synthesized in different temperatures, while compound (8a) can be obtained by the heating of compound (7) through crystal reassembly.
Compound (1)-(8) are all structurally characterized by single crystal Xray diffraction, and the magnetic properties.

摘要------------------------------------------------------ I
ABSTRACT---------------------------------------------- III
致謝----------------------------------------------------- V
圖目錄-------------------------------------------------- XII
表目錄------------------------------------------------- XIX
第一章 緒論-----------------------------------------------1
1-1 前言------------------------------------------1
1-2 自組裝合成法 (Self-assembly method)14------------ 3
1-3 超分子化學 (Supramolecular Chemistry)15,16--------- 4
1-3-1 π-π堆疊 (π-π stacking interaction)----------- 4
1-3-2 氫鍵 (Hydrogen Bonding, 4-120 kJ mol-1)-----5
1-4 磁性 (Magnetism)------------------------------ 6
第二章 實驗設計概念與實驗儀器藥品------------------------10
2-1 實驗設計概念---------------------------------10
2-2 實驗儀器藥品---------------------------------14
2-2-1 儀器-----------------------------------14
2-2-2 藥品-----------------------------------16
第三章 {[M(Me2mal)(bpy)0.5(H2O)]}n (M = Mn, Co, Ni) 合成與討論--------------------------------------------------17
3-1 化合物{[Mn(Me2mal)(bpy)0.5(H2O)]}n (1)----------17
3-1-1 合成----------------------------------17
3-1-2 單晶X-ray繞射結構分析---------------- 18
3-1-3 結構描述------------------------------22
3-1-4 熱重分析------------------------------26
3-1-5 粉末繞射------------------------------27
3-1-6 磁性測量------------------------------28
3-2 化合物{[Co(Me2mal)(bpy)0.5(H2O)]}n (2)---------- 34
3-2-1 合成----------------------------------34
3-2-2 單晶X-ray繞射結構分析---------------- 35
3-2-3 結構描述------------------------------39
3-2-4 熱重分析------------------------------43
3-2-5 粉末繞射------------------------------44
3-2-6 磁性測量------------------------------45
3-3 化合物{[Ni(Me2mal)(bpy)0.5(H2O)]}n (3)-----------49
3-3-1 合成----------------------------------49
3-3-2 單晶X-ray繞射結構分析---------------- 50
3-3-3 結構描述------------------------------54
3-3-4 熱重分析------------------------------58
3-3-5 粉末繞射------------------------------59
3-3-6 磁性測量------------------------------60
3-4 結論----------------------------------------65
第四章 {[Mn(H-Et2mal)2(bpy)(H2O)2]}n 及{[M2(Et2mal)2(bpy)2(H2O)2]•2H2O•2DMF}n (M = Co, Ni) 合成與討論--------------------------------------------66
4-1 化合物{[Mn(H-Et2mal)2(bpy)(H2O)2]}n (4)---------- 66
4-1-1 合成------------------------------------66
4-1-2 單晶X-ray繞射結構分析------------------ 67
4-1-3 結構描述--------------------------------71
4-1-4熱重分析-------------------------------- 77
4-2 化合物{[Co2(Et2mal)2(bpy)2(H2O)2]•2H2O•2DMF}n (5)-78
4-2-1 合成------------------------------------78
4-2-2 單晶X-ray繞射結構分析------------------ 79
4-2-3 結構描述--------------------------------85
4-2-4 熱重分析--------------------------------90
4-2-5 粉末繞射--------------------------------91
4-2-6 磁性測量--------------------------------92
4-3 化合物{[Ni2(Et2mal)2(bpy)2(H2O)2]•2H2O•2DMF}n (6)- 96
4-3-1 合成------------------------------------96
4-3-2 單晶X-ray繞射結構分析------------------ 97
4-3-3 結構描述-------------------------------102
4-3-4 熱重分析-------------------------------107
4-3-5 粉末繞射-------------------------------108
4-3-6 磁性測量-------------------------------109
4-4 結論-----------------------------------------115
第五章 {[Co(Me2mal)(dpe)0.5(H2O)]}n 及{[Co2(Me2mal)2(dpe)]}n合成與晶體重組討論-----------------------------------116
5-1 化合物{[Co(Me2mal)(dpe)0.5(H2O)]}n (7)----------- 116
5-1-1 合成-----------------------------------116
5-1-2 單晶Xray繞射結構分析----------------- 117
5-1-3 結構描述-------------------------------121
5-1-4 熱重分析-------------------------------124
5-1-5 粉末繞射-------------------------------125
5-1-6 磁性測量-------------------------------126
5-2 化合物{[Co2(Me2mal)2(dpe)]}n (8)-----------------130
5-2-1 合成-----------------------------------130
5-2-2 單晶X-ray繞射結構分析----------------- 133
5-2-3 結構描述-------------------------------137
5-2-4 熱重分析-------------------------------140
5-2-5 粉末繞射-------------------------------141
5-2-6 磁性測量-------------------------------142
5-3 結論-----------------------------------------146
第六章 總結---------------------------------------------147
參考文獻------------------------------------------------149
附錄----------------------------------------------------153

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