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姓名 吳宇哲(Yu-Che Wu) 查詢紙本館藏 畢業系所 化學學系 論文名稱 具有Quinoxaline結構之雙金屬無機液晶材料
(Columnar Bimetallomesogens: Copper Complexes Derived from Quinoxaline Ring)相關論文 檔案 [Endnote RIS 格式]
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摘要(中) 系列一為具有quinoxaline結構之無機液晶,此系列以化合物2 2,3-bis(3.4-dialkoxylphenyl)quinoxaline-6-carboxylic-[(2-hydroxy-4-alkoxylphenylimino)methyl]-phenyl esters為配位基,與過渡金屬銅、鋅及鈀配位形成無機液晶,所得之化合物皆以1H、13C-NMR及元素分析鑑定,並以DSC、偏光顯微鏡及POWDER X-RAY鑑定其液晶相。
錯合物形成具有8-10根側鏈基之雙金屬盤狀液晶,其中銅及鈀錯合物具有寬廣液晶範圍,在液晶相時形成hexagonal columnar phases (Colh)相,結構為型變平面四邊形配位;鋅錯合物則不具有液晶相產生。
系列二為具有benzoxazole 及quinoxaline 結構之有機分子,經由DSC、偏光顯微鏡及POWDER X-RAY鑑定後可以得知,化合物在液晶相時形成hexagonal columnar phases (Colh)盤狀液晶,其發光性質亦利用UV-Vis及螢光光譜鑑定,化合物之螢光發光來源為quinoxaline環,量子產率約為26 %。
系列三中合成並比較4種含benzylidene-aniline及quinoxaline環結構有機液晶分子,化合物在液晶相時形成hexagonal columnar phases (Colh)盤狀液晶,且可以發現化合物的澄清點溫度、液晶相時的排列、發光性質皆受到取代基的影響。摘要(英) In this thesis, we report the synthesis, characterization and mesomorphic properties of new mesogenic derivatives based on quinoxaline structure.
In series one , A new type of binuclear transition metal complexes derived from 2,3-bis(3.4-dialkoxylphenyl)quinoxaline-6-carboxylic-[(2 -hydrox y-4-alkoxylphenylimino)methyl]-phenyl esters was prepared and characterized. The mesomorphic properties of these copper comple -xes of were studied by differential scanning calorimetry (DSC) and polarized optical microscope (POM). These complexes have two metal centers as core group and have totally eight or ten alkoxy side chains appended around the central core forming a columnar molecule. All derivatives of copper(II) and palladium(II) compounds exhibited columnar mesophases over a wide range of temperatures. The geometries at metal centers is distorted square planar. The mesophases were identified as hexagonal columnar phases (Colh) based on the optical textures. Zinc(II) compounds don’t exhibited columnar mesophases.
In series two, we designed and characterized a series of new type of organic molecule derived from benzoxazole and quinoxaline rings with totally five side chains. Their mesomorphic properties were studied by differential scanning calorimeter (DSC) ,polarized optical microscopy (POM) and temperature dependent powder X-ray diffraction. Compounds exhibited columnar mesophases over a wide range of temperatures. Their luminescence properties were also studied by UV-Vis and fluorescence spectrometry. We found that fluorescent properties come form quinoxaline rings with Quantum yield about 26%.
In series three, we designed and characterized four kind of organic molecule derived from benzylidene-aniline and quinoxaline rings with totally five side chains. Their mesomorphic properties were studied by differential scanning calorimeter (DSC) ,polarized optical microscopy (POM) and temperature dependent powder X-ray diffraction. Compounds exhibited columnar mesophases over a wide range of temperatures. The clearing point, arrangement in mesophase, luminescence properties were found to be strongly dependent on the hydroxy group attached.關鍵字(中) ★ 盤狀液晶
★ 液晶
★ 無機液晶關鍵字(英) ★ metallomesogens
★ discotic liquid crystals
★ liquid crystals論文目次 中文摘要………………………………………………………………Ⅰ
英文摘要………………………………………………………………Ⅱ
謝誌……………………………………………………………………Ⅳ
目錄……………………………………………………………………Ⅴ
圖目錄………………………………………………………………ⅩⅠ
表目錄………………………………………………………………ⅩⅤ
附圖目錄……………………………………………………………ⅩⅥ
第一章 緒論……………………………………………………………1
1-1 液晶之簡介…..………………………………………………2
1-2 液晶分子結構之設計…………………………………3
1-3 液晶之分類…………………………………………………4
1-4 液晶的性質…………………………………………………12
1-5 無機液晶之特性……………………………………………14
1-6 盤狀液晶材料的研究及應用………………………………16
1-7 研究動機…………………………………………………19
第二章 實驗部分……………………………………………………24
2-1 實驗藥品……………………………………………………25
2-2 儀器設備………………………………………………26
2-3 實驗流程……………………………………………………34
2-3-1 系列一之實驗流程圖…………………………………34
2-3-2 系列二之實驗流程圖………………………………35
2-3-3 系列三之實驗流程圖………………………………36
2-4 實驗步驟………………………………………………………37
2-4-1 系列一之實驗步驟……………………………………37
2-4-1-1 3-Alkyloxyphenol之合成………………………37
2-4-1-2 5-Alkyloxy-2-nitrophenol之合成……………… 38
2-4-1-3 2-Amino-5-alkyloxyphenol之合成.…………… 38
2-4-1-4 1,2-bis(3,4-dialkoxyphenyl)-1,2-ethanedione之合成……………………39
2-4-1-5 2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylic acid之合成…………………………40
2-4-1-6 2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylic acid 4-formyl-3-hydroxy-phenyl ester之合成………………………………………………41
2-4-1-7 2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylic acid 4-[(4-alkoxy-2-hydroxy-phenylimino) -methyl]-3-hydroxy-phenyl ester之合成………42
2-4-1-8 Bis{2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylic acid4-[(4-alkoxy-2-hydroxy-pheny- limino)-methyl]-3-hydroxy-phenylester} copper(II) 之合成……………………………………………45
2-4-1-9 Bis{2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylic acid4-[(4-alkoxy-2-hydroxy-phenylim- ino)-methyl]-3-hydroxy-phenylester} palladium(II) 之合成……………………………………………47
2-4-1-10 Bis{2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylic acid4-[(4-alkoxy-2-hydroxy-pheny- limino)-methyl]-3-hydroxy-phenylester} zinc(II)之合成……………………………………………48
2-4-2 系列二之實驗步驟…………………………………49
2-4-2-1 4-Alkoxy-nitrobenzenes 之合成.……………….49
2-4-2-2 4-Alkoxy-phenylamines 之合成.……………49
2-4-2-3 2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylic acid4-formyl-phenyl ester之合成.………50
2-4-2-4 2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylicacid4-[(4-alkoxy-2-hydroxy-phenylimino) methyl]-phenyl ester之合成.…………………51
2-4-2-5 2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylic acid4-(6-alkoxybenzoxazol-2-yl)-phenyl ester之合成……………………………….55
2-4-3 系列三之實驗步驟…………………………58
2-4-3-1 2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylic acid 4-[(4-alkoxy-phenylimino)-methyl] -phenyl ester 之合成…………………58
2-4-3-2 2,3-Bis-(3,4-bis-dialkoxyphenyl)-quinoxaline-6-carboxylic acid 4-[(4-alkoxyphenylimino)-methyl]-3- hydroxy-phenyl ester 之………………….59
第三章 結果與討論……………………………………………………62
化合物結構與相對應代號……………………………………63
3-1 化合物結構之鑑定…………………………………64
3-1-1 元素分析(EA)及質譜(MS) ……………………64
3-1-2 單晶結構……………………………………66
3-1-3 電子順磁共振 (EPR)研究……………………67
3-2 結果與討論…………………………………………69
3-2-1 系列一配位基化合物2……………………69
3-2-1-1 相轉換行為……………………………………69
3-2-1-2 液晶相的鑑定………………………………… 71
3-2-1-3 FT-IR 研究…………………………………74
3-2-1-4 分子堆疊……………………………………76
3-2-2 系列一 錯合物1………………………………78
3-2-2-1 相轉換行為……………………………………78
3-2-2-2 液晶相的鑑定………………………………… 80
3-2-2-3 分子堆疊………………………………………84
3-2-3 系列二 化合物4…………………………………85
3-2-3-1 相轉換行為…………………………………85
3-2-3-2 液晶相的鑑定 ……………………………… 87
3-2-3-3 化合物4a之單晶結構研究………………90
3-2-3-4 FT-IR 研究 …………………………………93
3-2-3-5 分子推疊………………………………………95
3-2-4 系列二 化合物3………………………………96
3-2-4-1 相轉換行為…………………………………96
3-2-4-2 液晶相的鑑定………………………………98
3-2-4-3 分子推疊……………………………………100
3-2-4-4 吸收及放光光譜……………………………102
3-2-4-5 電化學特性…………………………………105
3-2-5 系列三 化合物之比較…………………………107
3-2-5-1 相轉換行為……………………………………107
3-2-5-2 液晶相的鑑定…………………………………109
3-2-5-3 FT-IR 研究 …………………………………112
3-2-5-4 分子堆疊………………………………………114
3-2-5-5 吸收及放光光譜………………………………115
3-2-5-6 電化學特性……………………………………118
3-3 結論……………………………………………………….121
3-3-1 系列一之結論…………………………………………121
3-3-2 系列二之結論………………………………………122
3-3-3 系列三之結論………………………………………123
參考文獻……………………………………………………………124
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