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系統識別號 U0002-0409201202100300
中文論文名稱 α-雙亞胺及苯甲酸為架構之鈷、鎳、銅、鋅金屬液晶
英文論文名稱 New Metallomesogens Based on Co(II), Ni(II), Cu(II), Zn(II) Complexes with α–Diimine Derivatives and 3,4,5-trialkoxybenzoate Ligand
校院名稱 淡江大學
系所名稱(中) 化學學系博士班
系所名稱(英) Department of Chemistry
學年度 100
學期 2
出版年 101
研究生中文姓名 林建合
研究生英文姓名 Chien-Ho Lin
學號 894170017
學位類別 博士
語文別 中文
口試日期 2012-07-18
論文頁數 178頁
口試委員 指導教授-王文竹
委員-林志彪
委員-賴重光
委員-李冠明
委員-王伯昌
委員-王文竹
中文關鍵字 金屬液晶  雙亞胺基配位子  苯甲酸長碳鏈 
英文關鍵字 Metallomesogens  α–Diimine Derivatives  3,4,5-trialkoxybenzoate Ligand 
學科別分類
中文摘要 以鈷、鎳、銅及鋅金屬離子與長碳鏈苯甲酸(3Cn)先合成出M-3Cn (n=16, 14, 12, 10)。M-3Cn再與α-雙亞胺基衍生物(3,6-PPA、2,5-PPZ及2,3-PPZ)合成出具有雙核且相異配位基系統的錯合物,M-L-3Cn。利用氫譜、元素分析、紅外線光譜及單晶結構分析對結構及純度作初步的鑑定。
藉由偏光顯微鏡、示差掃描卡計及變溫粉末x-ray繞射光譜來瞭解錯合物在不同溫度下的液晶性質。除了M-3Cn (Co、Ni及Zn)及Cu-3C16為Cubic液晶相,所有錯合物皆為Colh液晶相。由示差掃描卡計得知大部份化合物皆具有良好的熱穩定性而液晶溫度範圍很廣,在低碳數的化合物皆具有室溫液晶特性。
最後,透過變溫磁化率量測得知雙核錯合物(Co、Ni及Cu)中金屬間具有反鐵磁性作用力存在。特別的是這明顯的性質在Colh液晶溫度內就已經開始存在。
英文摘要 Metal complexes of general formula M-3Cn based upon substituted 3,4,5-trialkoxybenzoate (3Cn, n=16, 14, 12, 10) and with Co, Ni, Cu and Zn have been prepared. Reaction of M-3Cn with α-diimine derivatives (L=3,6-PPA, 2,5-PPZ, 2,3-PPZ) leads to the dinuclear heterolytic complexes M-L-3Cn. 1H-NMR, EA, IR and single crystal X-ray analysis were employed to study the structure and purity of these complexes.
The liquid crystalline character of the synthesized compounds has been studied by polarized optical microscopy, differential scanning calorimetry, and variable temperature X-ray diffraction . They all exhibit thermotropic Colh mesophases except the M-3Cn derivatives(Co, Ni, Zn) and Cu-3C16 exhibit a cubic mesophases. In some cases, the high thermal stability of the compounds leads to rather extended mesomorphic ranges and exhibit room temperature.
Finally, variable temperature magnetic susceptibility measurements of dinuclear complexes show anti-ferromagnetic coupling between adjacent metal ions (Co, Ni and Cu). Noticeably, the existence of the distinct magnetic coupling is among the Colh temperature.
論文目次 中文摘要....................................................I
英文摘要...................................................II
第一章 緒論
1-1 液晶的簡介………….……………......................……………………………………1
1-2 液晶的基本架構…………………………………………......……............………....3
1-3 金屬液晶.............................……………..........…………4
1-3-1 金屬液晶之特性…………………………………………………………...................5
1-3-2金屬液晶之回顧……………………………………………………………..............5
1-4 研究動機……………………………………………………………….......................12
第二章 實驗
2-1 實驗藥品………………. …………………………………………...………................…14
2-2 儀器設備............................. ……..............…16
2-3 合成流程圖…………………………………...……………………………….................19
2-4 化合物的合成...…......................... ……...…………………… 22
2-4-1化合物3,6-bis-(2’-pyridyl)pyridazine的合成……....…………… 22
2-4-2化合物2,5-bis-(2’-pyridyl)pyrazine的合成…………..……….……. 23
2-4-3化合物2,3-bis-(2’-pyridyl)pyrazine的合成……….….…….………..26
2-4-4化合物Methyl 3,4,5-tris(alkyloxy)benzoate的合成……….………27
2-4-5化合物3,4,5-tris(alkyloxy)benzoate, sodium的合成..…..…28
2-4-6化合物Bis(3,4,5-tris(alkyloxy)benzoate) cobalt(II)的合
成…................................................ 30
2-4-7化合物Bis(3,4,5-tris(alkyloxy)benzoate) nickel(II)的合
成…........................................……………... 31
2-4-8化合物Bis(3,4,5-tris(alkyloxy)benzoate) copper(II)的合
成..........................................….…………….32
2-4-9化合物Bis(3,4,5-tris(alkyloxy)benzoate) zinc(II)的合成33
2-4-10化合物(3,6-bis-(2’-pyridyl)pyridazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dicobalt(II)的合成.........…34
2-4-11化合物(3,6-bis-(2’-pyridyl)pyridazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dinickel(II)的合成…........…35
2-4-12化合物(3,6-bis-(2’-pyridyl)pyridazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dicopper(II)的合成.........…36
2-4-13化合物(3,6-bis-(2’-pyridyl)pyridazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dizinc(II)的合成…..........…37
2-4-14化合物(2,5-bis-(2’-pyridyl)pyrazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dicobalt(II)的合成…........…37
2-4-15化合物(2,5-bis-(2’-pyridyl)pyrazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dinickel(II)的合成….........38
2-4-16化合物(2,5-bis-(2’-pyridyl)pyrazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dicopper(II)的合成….........39
2-4-17化合物(2,5-bis-(2’-pyridyl)pyrazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dizinc(II)的合成…..........…39
2-4-18化合物(2,3-bis-(2’-pyridyl)pyrazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dicobalt(II)的合成…........…40
2-4-19化合物(2,3-bis-(2’-pyridyl)pyrazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dinickel(II)的合成…........…41
2-4-20化合物(2,3-bis-(2’-pyridyl)pyrazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dicopper(II)的合成…........…42
2-4-21化合物(2,3-bis-(2’-pyridyl)pyrazine)-bis(3,4,5-
tris(alkyloxy)benzoate) dizinc(II)的合成…..........…42

第三章 結果與討論
3-1化合物之合成………….……......…………………………....................… 44
3-1-1 配位子之合成………………………..........…………………………….......…....44
3-1-2 錯合物之合成……………………………………………….............…….......……46
3-2化合物之鑑定………….……...........……………....................… 48
3-2-1 化合物之氫譜……………………………………..............………………….......48
3-2-2 化合物之元素分析……………………………………………………...................51
3-2-3 化合物之紅外線光譜…………………………………………………..................52
3-2-4 化合物之單晶X-ray結構…………………………………………..................55
3-3化合物M-3Cn之液晶性質探討…………..........................…… 92
3-3-1 M-3Cn之偏光紋理圖…………..………………..…...............……92
3-3-2 M-3Cn之熱分析探討………………..……………………...............…95
3-3-3 M-3Cn之變溫X-ray繞射探討………………………................99
3-4化合物M-3,6-PPA-3Cn之液晶性質探討……….....................109
3-4-1 M-3,6-PPA-3Cn之偏光紋理圖…......…………………………………………109
3-4-2 M-3,6-PPA-3Cn之熱分析探討…………………...…..…………………..…112
3-4-3 M-3,6-PPA-3Cn之變溫X-ray繞射探討………..…………………....117
3-4-4 M-3,6-PPA-3Cn之堆疊模型的理論計算探討….…………………....123
3-5化合物M-2,5-PPZ-3Cn之液晶性質探討………….……………..............126
3-5-1 M-2,5-PPZ-3Cn之偏光紋理圖……………………………...………..…..…126
3-5-2 M-2,5-PPZ-3Cn之熱分析探討……………………..………….....…………129
3-5-3 M-2,5-PPZ-3Cn之變溫X-ray繞射探討…………..……………..…..134
3-5-4 M-2,5-PPZ-3Cn之堆疊模型的理論計算探討…....………..…..139
3-6化合物M-2,3-PPZ-3Cn之液晶性質探討………….……………..…...........142
3-6-1 M-2,3-PPZ-3Cn之偏光紋理圖…………………………...…………..…..…142
3-6-2 M-2,3-PPZ-3Cn之熱分析探討……………………..………...…………..…145
3-6-3 M-2,3-PPZ-3Cn之變溫X-ray繞射探討…………..………………....150
3-6-4 M-2,3-PPZ-3Cn之堆疊模型的理論計算探討…..……………..…..155
3-7化合物之磁性探討………….…….....................……...........158
3-7-1 M-3Cn之磁性分析………………..............………………..…..…161
3-7-2 M-3,6-PPA-3Cn之磁性分析……………….....…………….…..…..…162
3-7-3 M-2,5-PPZ-3Cn之磁性分析……………….……….......…..…..…165
3-7-4 M-2,3-PPZ-3Cn之磁性分析……………….….......………..…..…168

第四章 結論……………………………................……............…………172

第五章 參考文獻………………………………............. ............…………174
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