以1,3,4-thiadiazole為架構之不對稱無機液晶材料

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姓名

廖政宗(Cheng-Tsung Liao) 查詢紙本館藏

畢業系所

化學學系

論文名稱

以1,3,4-thiadiazole為架構之不對稱無機液晶材料
(Synthesis and Characterization of Copper(Ⅱ) Complexes Derived from 1,3,4-Thiadiazole-based Containing Asymmetric Cores)

相關論文

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★ 以1,3,4-thiadiazole為架構之無機盤狀液晶材料	★ 以benzoxazole為架構之無機桿狀液晶
★ 具有Quinoxaline結構之雙金屬無機液晶材料	★ 星型液晶材料及磷光發光材料之合成與研究
★ 含pyrazole及isoxazole之有機桿狀液晶	★ 矽咔哚與矽螺旋雙笏物質之放光性質研究
★ 具有Benzobisthiazoles和Benzobisoxazoles結構之盤狀液晶材料	★ 含 Benzoxazole 之對稱二聚物其奇偶效應的探討
★ 以電腦模擬研究香蕉型液晶元的分子交互作用力	★ 極性取代基對於彎曲型液晶分子的影響
★ 由彎曲型分子形成盤狀液晶之探討	★ 含cis-enaminoketone 結構的無機液晶材料

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摘要(中)

近幾年來含雜環的液晶分子已經被廣泛的研究，而本篇論文系列一設計並合成含thiadiazole之不對稱的配位基及其相對應金屬錯合物，系列二則為含Benzoxazole之對稱二聚物結構。本實驗所合成之化合物皆由1H與13C-NMR光譜及元素分析(EA)來鑑定分子的結構與純度，液晶相性質由偏光顯微鏡來觀察偏光紋理圖，再以熱差式掃描卡計儀測定相變化，最後以變溫粉末X-ray繞射鑑定其液晶相的結構。
系列一的實驗結果顯示配位基與錯合物皆呈現了桿狀的液晶相，其液晶相為N、SmA與SmC，可以發現這些化合物的液晶相性質跟侧鏈基的碳鏈長短有關，隨著碳鏈的減少澄清點與熔點的溫度增加，另外錯合物的澄清點明顯比配位基來的高許多。
系列二的實驗結果顯示了所有的化合物皆為規則度較好的SmC相，且當固定中間橋接基時，隨著側鏈基碳鏈增加澄清點溫度相上升，而令人值得注意的是此系列的分子有明顯的奇偶效應。

摘要(英)

The design and synthesis of liquid crystals (LCs) containing heterocyclic units have been the subject of much research in recent years. Series Ⅰ: design and synthesis of Copper(Ⅱ) complexes derived from 1,3,4- thiadiazole-based containing asymmetric cores. Series Ⅱ: a novel system of symmetric dimmer liquid crystals containing benzoxazole units. All compounds were all characterized by 1H and 13C-NMR spectroscopy , their mesomorphic properties were studied by differential scanning calorimeter (DSC) ,polarized optical microscopy (POM) and temperature dependent powder X-ray diffraction.
Experimental data indicated that series Ⅰ, all compounds exhibited, nematic(N), smectic A (SmA) and/or smectic C (SmC) phases, as expected by rod-like molecules. In addition, the mesomorphic properties observed by these compounds were found to be strongly dependent on the carbon chain length of terminal side chains. Both the melting and clearing points were increased with decreasing the carbon chain length. The transition temperatures of these rod-like metallo- mesogens are higher than those of the corresponding metal-free ligands. In the series Ⅱ, all compounds exhibited smectic C (SmC) phase, and when we fix the carbon number of the spacer, clearing points increased with increasing the carbon number of side chain. Odd-even effect could also be observed obviously in series Ⅱ.

關鍵字(中)

★ 液晶

關鍵字(英)

★ liquid crystal
★ thiadiazole

論文目次

目錄
中文摘要………………………………………………………………..Ⅱ
英文摘要………………………………………………………………..Ⅲ
謝誌………………………………………………………………….….Ⅳ
目錄……………………………………………………………………..Ⅴ圖目錄………………………………………………………………..ⅩⅠ
表錄………………………………………………………………......ⅩⅤ
附圖目錄…………………………………………………………..ⅩⅤⅠ
第一章緒論……………………………………………...….…………..1
1-1 前言……………………………….……………….……..……….…2
1-2 液晶之起源及簡介……………………………….…..……………..3
1-3液晶分子之基本架構與物理性質….……….……….……………...5
1-4液晶的分類…….………………………….…...…….........................9
1-5氫鍵型液晶………………..…………..………………………........16
1-6 Dimeric liquid crystals之結構組成及特性…..…….…………........22
1-7研究動機………………………………………………………........28
1-7-1系列一與系列二之研究動機………………………………….…28
1-7-2系列三之研究動機.……….………..….....….…………………...35
第二章實驗部份………………………………………………....……37
2-1 實驗藥品………………………………………………..…….........38
2-2 實驗儀器…….…………………………………………....………..41
2-3 實驗流程……………………………………………........………...44
2-3-1化合物結構與相對應代號一覽表……………….………………44
2-3-2系列一化合物合成流程……………………….............................45
2-3-3系列二化合物合成流程……………………….…………………46
2-3-4系列三之一化合物合成流程…………………………………….47
2-3-5系列三之二化合物合成流程…………………………………….48
2-4 實驗步驟……………………………………………………..…….50
2-4-1系列一、系列二之實驗步驟…………………………………….50
2-4-1-1 Methyl 4-(alkoxy)-2-hydroxybenzoate之合成…….…...……...50
2-4-1-2 4-Alkoxy-2-hydroxybenzaldehydes之合成…….….…………..51
2-4-1-3 4-(Alkoxy)benzaldehyde之合成.................................................51
2-4-1-4 Methyl 4-(Alkoxy)-2-hydroxybenzoic acid hydrazide之合成...52
2-4-1-5 6-(Alkoxy)naphthalene-2-carboxylic acid之合成….………….53
2-4-1-6 Methyl 6-(Alkoxy)naphthalene-2-carboxylate之合成………...54
2-4-1-7 6-(Alkoxy)naphthalene-2-carbohydrazide之合成……….…….55
2-4-1-8 4-(Alkoxy)benzoic acid之合成………………………………..56
2-4-1-9 6-(Alkoxy)naphthalene-2-carboxylicacid
N-(4-(alkoxy)-2-hydroxybenzoyl)hydrazide之合成…………...………56
2-4-1-10 6-(Alkoxy)naphthalene-2-carboxylic acid N-(2-hydroxy benzoyl)hydrazide之合成..…………………………………………….59
2-4-1-11 4-(Alkoxy)benzoic acid N-(2-hydroxybenzoyl)hydrazide之合成………………………………………………………………………..61
2-4-1-12 2-Naphthoic acid N-(4-(alkoxy)-2-hydroxybenzoyl) hydrazide之合成………………………………………………………………..…61
2-4-1-13 5-(Alkoxy)-2-(5-(2-(alkoxy)naphthalen-6-yl) -1,3,4- thiadiazol-2-yl) phenol之合成…............................................................62
2-4-1-14 2-(5-(2-(Alkoxy)naphthalen-6-yl)-1,3,4-thiadiazol-2-yl)phenol之合成…………………………………………………...……………...65
2-4-1-15 2-(5-(4-(alkoxy)phenyl)-1,3,4-thiadiazol-2-yl)phenol之合成…………………………………………………………………..……67
2-4-1-16 5-(Alkoxy)-2-(5-(naphthalen-2-yl)-1,3,4-thiadiazol-2-yl)phenol之合成……………………………………………………………….….67
2-4-1-17 Bis(5-(alkoxy)-2-(5-(2-(alkoxy)naphthalen-6-yl)-1,3,4- thiadiazol-2-yl)phenol)copper(II)之合成………………………………69
2-4-1-18 Bis(2-(5-(2-(Alkoxy)naphthalen-6-yl)-1,3,4-thiadiazol-2-yl) phenol) copper(II)之合成……………………………………………….71
2-4-1-19 Bis(5-(Alkoxy)-2-(5-(naphthalen-2-yl)-1,3,4-thiadiazol-2-yl) phenol) copper(II)之合成………………………………………………72
2-4-1-20 (E)-N'-(4-(alkoxy)benzylidene)-6-(alkoxy)naphthalene-2- carbohydrazide之合成…………………………………………………73
2-4-1-21 (E)-N'-(4-(alkoxy)-2-hydroxybenzylidene)-6-(alkoxy)
naphthalene-2-carbohydrazide之合成…………………………………74
2-4-1-22 6-(Alkoxy)naphthalene-2-carboxylicacidN-(4-dodecyloxy benzoyl) hydrazide之合成………………………………………..……75
2-4-2系列三之一、系列三之二之實驗步驟……...………………….77
2-4-2-1 3-Alkoxyphenols之合成……………………………………….77
2-4-2-2 1,2-Didodecyloxy-4-nitrobenzene之合成…………..…….…...77
2-4-2-3 2-Amino-5-Alkoxyphenols之合成……………...….................78
2-4-2-4 Bis(4-formylphenyl) alkanedioate之合成……….....................79
2-4-2-5 Bis(4-((E)-(4-(alkoxy)-2-hydroxyphenylimino)methyl)phenyl) alkanedio ate之合成………...................................................................80
2-4-2-6 Bis(4-(6-(alkoxy)benzoxazole-2-yl)phenyl) alkanedioate之合成….........................................................................................................82
2-4-2-7 4-Formylphenyl acetate之合成………….………………...….89
2-4-2-8 4-((E)-(4-(alkoxy)-2-hydroxyphenylimino)methyl)phenyl acetate之合成…………………………………………....………………….….89
2-4-2-9 4-(6-(alkoxy)benzo[d]oxazol-2-yl)phenyl acetate之合成.........90
2-4-2-10 4-(6-(Alkoxy)benzo[d]oxazol-2-yl)phenol之合成…………...91
2-4-2-11 Bis(4-(6-(alkoxy)benzoxazole-2-yl)phenyl) alkanedioate之合成………………………………………………………………………..92
第三章實驗結果與討論………………………………………………95
3-1 反應機構之探討………………………………………….…….….96
3-1-1醚化反應…………………………………………….….…..…….96
3-1-2硝化反應…………………………………………….….…..…….97
3-1-3還原反應………………………………….…………..….……….98
3-1-4 Schiff base反應………………………………………….……….99
3-1-5 Benzoxazole合環反應………………………..………….……..100
3-1-6 1,3,4-thiadiazole合環反應…………………………….…..……101
3-2 實驗結果討論………………………..…………………….……..103
3-2-1系列一、系列二之結果討論………………...…………….…...103
3-2-1-1系列一、系列二化合物之結構鑑定……………....................104
3-2-1-2系列一、系列二液晶相性質之鑑定與探討………….…..….112
3-2-1-3其他物性的探討………………………………………..……..138
3-2-2系列三之一、系列三之二之結果討論…………………..….…143
3-2-2-1合成策略的討論………………………………………..……. 143
3-2-2-2系列三之一、系列三之二化合物之結構鑑定……………….144
3-2-2-3系列三之一、系列三之二液晶相性質之鑑定與探討……….147
3-3 結論…………………….…..……………………………………..156
3-3-1系列一與系列二之結論………………………………………...156
3-3-2系列三之結論…………………………………………………...156
參考文獻………………………………………………………………157
附圖……………………………………………………………………163

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指導教授

賴重光(Chung-Kung Lai)

審核日期

2005-7-14

推文