含雙金屬無機液晶之設計與物性探討｜國立中央大學博碩士論文系統

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研究生：	鄭元輔 Yuan-Fu Cheng
論文名稱：	含雙金屬無機液晶之設計與物性探討 The studies of bimetallmesogens
指導教授：	賴重光 C. K. Lai
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
畢業學年度：	92
語文別：	中文
論文頁數：	154
中文關鍵詞：	雙金屬、液晶
外文關鍵詞：	bimetallmesogens
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本篇論文以合成三系列具不同結構形式之配位基及其金屬錯合物，與分別探考其可能之液晶相行為及性質。此三系列分為：系列一dicopper (II) complexes of 3, 4, 5-trialkoxybenzoicacid-(2-hydroxy-4- alkoxybenzyidine)hydrazides，系列二dicopper (II) complexes of 4-(tetra decanoxy-benzoicacid4-[(3,4-dialkoxybenzoyl)hydrazonomethy]-3- hydroxyphenyl esters，以及系列三2, 6-bis-(3, 4, 5-trialkoxyphenyl)- benzo[1, 2-d; 5, 4-d’]bisoxazoles。
於分子結構設計中，我們藉著改變兩邊側鏈柔軟支鏈之碳鏈長度、支鏈數目與配位基中段連接基種類，來探討其對液晶相形成所產生之影響。實驗藉1H及13C-NMR光譜來鑑定合成化合物之結構，並由元素分析值以確定錯合物之純度。於液晶相行為之探討部分，我們藉偏光顯微鏡下對不同相溫度變化範圍及液晶相種類作一初步觀察，再以DSC熱分析儀對相變化溫度及熱含量變化判別。
實驗結果得知，系列一之dicopper (II) complexes of 3,4,5-tri alkoxybenzoicacid -(2-hydroxy-4-alkoxybenzyidine)hydrazides，當其側鏈基數目為六或八根時，此系列之化合物皆為盤狀液晶，液晶相結構為Colh phase。於系列二dicopper (II) complexes of 4-(tetradecanoxy- benzoicacid4-[(3,4-dialkoxybenzoyl)-hydrazonomethy]-3-hydroxyphenyl esters；當化合物中間連接基為醚化基時，側邊只需六根側鏈基便具液晶相，然而，中間連接基為酯化基時，側邊則需增加至十根側鏈基才具液晶相，其二者之液晶相結構皆為Colh phase。系列三2, 6-bis(3, 4, 5-trialkoxphenyl)benzo[1, 2-d; 5, 4-d’]bisoxazoles，側鏈基之alkoxy groups碳數為n = 8、10、12或14時，皆具有Colh之液晶相。

This thesis describes the synthesis, characterization and meso- morphic properties of three series (Series I , II , III) of organic ligands and their copper(II) complexes. These compounds include; Series I dicopper (II) complexes of 3, 4, 5-trialkoxybenzoic acid-(2-hydroxy-4- alkoxybenzyidine)hydrazides; Series II dicopper (II) complexes of 4-(tetradecanoxybenzoicacid4-[(3, 4-dialkoxybenzoyl)hydrazonomethy] -3-hydroxyphenyl esters and Series III: 2, 6-bis-(3,4,5-trialkoxphenyl) benzo[1, 2-d; 5, 4-d’]bisoxazoles.
By molecular modification of the carbon chain lengths, the number of the terminal flexible side chains and/or the linkers, the mesomorphic properties observed by these compounds were characterized and also studied in detail. For the spectroscopic characterization of all compounds, 1H and 13C NMR spectra were used to identify the structure and the purity of the compounds, and elemental analysis was also used to confirm the purity. DSC thermal analysis and optical polarised microscopy were used to characterize and confirm the structure of the liquid crystalline mesophases.
The data indicated that for the Series I, dicopper (II) complexes of 3, 4, 5-trialkoxybenzoic acid-(2-hydroxy-4-alkoxybenzyidine)hydrazides, when the numbers of the terminal flexible side chains were either six or eight these copper complexes exhibited Colh phase. The Colh phases were observed for the Series II, dicopper (II) complexes of 4-(tetradeca noxybenzoic acid 4-[(3, 4-dialkoxybenzoyl)hydrazonomethy]-3-hydroxy phenyl esters with the ether group as linker, when the carbon numbers is six, however, the same Colh phases were also formed for the copper(II) complexes with ester group as linker and side chains of ten. For the series III, 2, 6-bis-(3,4,5-trialkoxphenyl)benzo[1,2-d; 5, 4-d’]bisoxazole, these compounds exhibited Colh phases when the carbon numbers of the terminal flexible side chains are 8, 10, 12 and 14

中文摘要……………………………………………………I
英文摘要………………………………………………………………...II
謝誌……………………………………………………………………III
目錄……………………………………………………………………..IV
圖目錄……………………………………………………………VII
表目錄…………………………………………………………………..XI
附圖目錄……………………………………………………………XII
第一章	緒論
1-1	前言……………………………………………………………2
1-2	液晶之發現與形成…………………………………………2
1-3	液晶形成之要件……………………………………………4
1-4	液晶之性質……………………………………………………4
1-5	無機液晶之特性………………………………………………6
1-6	無機液晶的設計………………………………………………8
1-7	研究動機………………………………………………………8
第二章	實驗部份
2-1	實驗藥品……………………………………………………21
2-2	儀器設備……………………………………………………22
2-3	實驗流程……………………………………………………23
2-4	實驗步驟……………………………………………………29
2-4-1	系列一之合成步驟…………………………………………29
2-4-1-1	Methyl-3, 4, 5-trialkoxybenzoates之合成………………29
2-4-1-2	Ethyl-3, 4-dialkoxybenzoates之合成…………31
2-4-1-3	3, 4, 5-Trialkoxybenzoic acids之合成…………………32
2-4-1-4	3, 4-Dialkoxybenzoic acid之合成………………………34
2-4-1-5	3, 4, 5-Trialkoxybenzoic acid hydrazides之合成………35
2-4-1-6	3, 4-Dialkoxybenzoic acid hydrazide之合成…………37
2-4-1-7	4-Alkoxy -2-hydroxybenzaldehyde之合成……………...38
2-4-1-8	3, 4-Dialkoxybenzoicacid-(2-hydroxy-4-dodecanoxybenzyidine)hydrazides之合成………………………………..39
2-4-1-9	3, 4, 5-Trialkoxybenzoicacid-(2-hydroxy-4-dodecanoxybenzyidine)hydrazides之合成……………………………..42
2-4-1-10	Dicopper (II) complexes of 3, 4, 5-trialkoxybenzoicacid -(2-hydroxy-4-alkoxybenzyidine)hydrazides之合成…47
2-4-2	系列二之合成步驟………………………………………50
2-4-2-1	Methyl-4-alkoxybenzoates之合成………………………50
2-4-2-2	4-Tetradecanoxybenzoic acid之合成……………………50
2-4-2-3	4-Tetradecanoxybenzoyloxy salicylaldehyde…………….51
2-4-2-4	3, 4, 5-Tritetradecyloxy 4-acetyl-3-hydroxy-phenyl ester52
2-4-2-5	4-Tetradecanoxybenzyl alcohol…………………………52
2-4-2-6	4-Tetradecanoxybenzyl chloride…………………………53
2-4-2-7	2-Hydroxy-4-(tetradecanoxybenzyloxy)benzaldehyde…..53
2-4-2-8	4-(Tetradecanoxy-benzoicacid4-[(3,4-dialkoxybenzoyl)hydazonomethy]-3-hydroxyphenyl ester…………………….54
2-4-2-9	3, 4, 5-Tritetradecanoxybenzoicacid4-[3, 4-dialkoxyben zoyl]hydrazonomethy]-3-hydroxyphenylester…………56
2-4-2-10	4-(Tetradecanoxybenzoicacid4-[(3,4-dialkoxybenzoyl) hydrazonomethy]-3-hydroxyphenyl ester……………….57
2-4-2-11	Dicopper(II) complexes of 4-(tetradecanoxybenzoicac
id4-[(3,4-dialkoxybenzoyl)hydrazonomethy]-3-hydroxyphenyl ester之合成………………………………………….60
2-4-3	系列三之合成步驟………………………………………...62
2-4-3-1	2, 6-Bis-(3, 4, 5-trialkox-phenyl)-benzo[1, 2-d; 5, 4-d’]bisoxazole之合成…………………………………62
第三章	實驗結果與討論
3-1	實驗合成與反應機構之探討………………………………67
3-2	結果討論…………………………………………………….70
3-3	結論………………………………………………………….99
參考文獻……………………………………………………………...101
附圖

                                

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