含Ferrocene單取代液晶合成

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姓名

沈玟呈(Cheng-Wen Shen) 查詢紙本館藏

畢業系所

化學學系

論文名稱

含Ferrocene單取代液晶合成
(Synthesis of the monosubstituted ferrocenomesogens)

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摘要(中)

本論文主要是探討含ferrocene unit之液晶材料的合成與物性。藉由改變柔軟長碳鏈之長度，及堅硬的核心(rigid core)數目，來觀察液晶相的形成與否。本實驗所合成之化合物藉由1H-NMR與13C-NMR光譜及元素分析來鑑定分子結構與純度。液晶現象的觀察是藉由偏光顯微鏡(POM)來觀察其光學紋理圖，再利用熱差式掃瞄卡計(DSC)來測定其相變化時之熱焓值變化，最後以變溫粉末X光繞射儀鑑定液晶相結構。
在此論文中，我們合成出ferrocene unit接在桿狀型含pyrazole結構的有機液晶原末端，利用pyrazole間的氫鍵(NH----N)提供較強之分子間吸引力，抵抗ferrocene所造成的立體排斥，進而形成液晶相。實驗結果顯示，因ferrocene的立體排斥，使得分子不利於堆疊，形成液晶相範圍較窄的SmA相(約14~30 ℃)，且側鏈基之碳氫數長短對液晶相範圍沒太大影響。當改變pyrazole在液晶原的結構位置(與ferrocene的相對位置)，對分子間的吸引力有所改變，而出現不同的液晶相，且液晶相範圍亦有明顯差異。當增加液晶原的rigid core，即增加分子間的吸引力，可得到一極穩定且液晶相範圍較廣(平均約100 ℃)的N與SmC相

摘要(英)

Studies focused on synthesis and mesomorphic properties of ferrocene-based metallomesogens have gained increasing importance in recent years. Ferrocene, because of its aromatic character, facilitates several substitution reactions whereby a range of low molecular mass calamitic (rod-like) systems can be prepared by monosubstitution, disubstitution of 1,1’-, 1,2-, 1, 3-position, or 1,1,3-trisubstitution on the ferrocene molecules. In reported ferrocenyl systems, most liquid-crystalline behaviour has been found to exhibit nematic (N), smectic A (SmA) or smectic C (SmC). The mesomorphic behavior may be due to the size of the ferrocene unit, in which two cyclopendienyl rings sterically interfere with the packing of the molecules, thereby preventing the build-up of long-range order that would result in the formation of a softer crystal phase.
We describe herein the synthesis and mesomorphic of the mono substituted ferrocenecontaining liquid crystals. Their mesomorphic properties were investigated by use of polarized optical microscopy and differential scanning calorimetry(DSC). All the prepared compounds exhibit a smectic A mesophase.

關鍵字(中)

★ 液晶

關鍵字(英)

★ pyrazole
★ Ferrocene
★ metallomesogens
★ calamitic

論文目次

目錄
謝誌…………………………………………………………..………….I
中文摘要………………………………………………………………...II
英文摘要..................................................................................................III
目錄……………………………………………………………………..IV
圖目錄.....................................................................................................VII
表目錄......................................................................................................IX
附圖目錄...................................................................................................X
第一章緒論……………………………………………………………..1
1-1 前言………………………………………………………………..2
1-2 液晶之起源與簡介..........................................................................3
1-3 液晶分子結構之設計……………………………………………..4
1-4 液晶的分類………………………………………………………..5
1-5 液晶的性質………………………………………………………12
1-6 無機液晶的設計與分類…………………………………………14
1-7 無機液晶之特性…………………………………………………15
1-8 研究動機…………………………………………………………16
第二章實驗部分………………………………………………………..21
2-1 實驗藥品…………………………………………………………22
2-2 儀器設備…………………………………………………………23
2-3 實驗流程…………………………………………………………30
2-4 實驗步驟…………………………………………………………35
2-4-1-1 Methyl-4-alkoxybenzoate…………………………………….35
2-4-1-2 4-Alkoxybenzyl alcohol……………………………………...36
2-4-1-3 4-Alkoxybenzyl chloride……………………………………..36
2-4-1-4 4-Alkoxybenzylacetonephone………………………………..37
2-4-1-5 Ethyl 4-ferrocenylbenzoate…………………………………..38
2-4-1-6 1-[4-(4-Alkoxybenzyloxy)phenyl]-3-(4-ferrocenylphenyl) propane-1,3-dione………………………………………….....39
2-4-1-7 5-[4-(4-Alkoxybenzyloxy)phenyl]-3-(4-ferrocenylphenyl)-1H- pyrazole………………………...…………………………….40
2-4-1-8 1-[4-(4-alkoxybenzyloxy)phenyl]-3-phenylpropane -1,3-dione..…………………………………………………....41
2-4-1-9 5-[4-(4-alkoxybenzyloxy)phenyl]-3-phenyl-1H-pyrazole…...42
2-4-2-1 4-Alkoxyacetophenones………………………………….…..43
2-4-2-2 (4-ferrocenylphenyl)methanol………………………………..44
2-4-2-3 1-Chloromethyl-4-ferrocenylbenzene………………………..45
2-4-2-4 4-(4-ferrocenylbenzyloxy)benzoic acid methyl ester………...45
2-4-2-5 1-[4-(4-ferrocenylbenzyloxy)phenyl]-3-(4-alkoxyphenyl)
propane-1,3-dione…………………………………………….46
2-4-2-6 3-[4-(4-ferrocenylbenzyloxy)phenyl]-5(4-alkoxyphenyl)-1H-
pyrazole……………………………………………………....47
2-4-2-7 Bis[1-[4-(4-ferrocenylbenzyloxy)phenyl]-3-(4-alkoxyphenyl) propane-1,3-dione] copper(II)………………………………..49
2-4-2-8 1-[4(4-alkoxybenzyloxy)phenyl]-3-[4-(4-ferrocenyl phenyl)
propane-1,3-dione…………………………………………….50
2-4-2-9 5-[4-(4-alkoxybenzyloxy)phenyl]-3-[4-(4-ferrocenylbenzyloxy) phenyl]-1H-pyrazole………………………………………….51
第三章實驗結果與討論………………………………………………..53
3-1 實驗合成與反應機構之探討…………………………………….54
3-2 化合物之鑑定……………………………………………………58
3-3-1 Compound A之結果與討論……………………………………..59
3-3-1-1 偏光顯微鏡之觀察……………………………………………60
3-3-1-2 熱分析圖譜……………………………………………………63
3-3-1-3 powder X-ray繞射儀…………………………………………..64
3-3-1-4 元素分析數據…………………………………………………65
3-3-2 Compound B之結果與討論……………………………………..66
3-3-2-1 偏光顯微鏡之觀察……………………………………………66
3-3-2-2 熱分析圖譜……………………………………………………67
3-3-3 Compound C之結果與討論……………………………………..68
3-3-3-1 偏光顯微鏡之觀察……………………………………………69
3-3-3-2 熱分析圖譜……………………………………………………71
3-3-3-3 元素分析數據…………………………………………………72
3-3-4 Compound D之結果與討論……………………………………..73
3-3-5 Compound E之結果與討論……………………….……………..75
3-3-5-1 偏光顯微鏡之觀察……………………………………………76
3-3-5-2 熱分析圖譜……………………………………………………76
3-4 結論……………………………………………………………….80
參考文獻………………………………………………………………..81
圖目錄
圖1. 形成液晶的條件………………..………………………………….4
圖2. 液相性液晶與熱相性液晶……..………………………………….2
圖3. 桿狀液晶之基本化學結構…..…………………………………….6
圖4. 盤狀液晶形成之基本方式…………………………………..…….9
圖5. 盤狀液晶之堆疊方式…………………………………………….10
圖6. Colh之二種排列…………………………………………………..10
圖7. 氫鍵液晶分子…………………………………………………….11
圖8. 液晶光學特性…………………………………………………….13
圖9. 光的折射………………………………………………………….14
圖10. 含ferrocene液晶分子結構設計………………………...………17
圖11. 含ferrocene液晶分子…………………………………………..18
圖12. X-ray之繞射原理………………………………………………..27
圖13a. Colh排列與各晶面之俯面圖…………………...……………...28
圖13b. Colr排列與各晶面之俯視圖…………………………………...29
圖14. compound A結構圖……………………………………………...59
圖15. dimer之結構圖…………………………………………………..60
圖16. compound A(n = 8)之光學紋理圖…...………………………….62
圖17. compound A(n = 12)之光學紋理圖……………………………..62
圖18. 相變化溫度與碳鏈長之柱狀圖…………...……………………64
圖19. compound A(n = 16)之X-Ray圖…………………………..…….65
圖20. compound B結構圖…...…………………………………………66
圖21. compound B(n = 12)之光學紋理圖…...………………………...67
圖22. 相變化溫度與碳鏈長之柱狀圖……..………………………….68
圖23. compound C結構圖…...…………………………………………69
圖24. compound C (n = 12)之光學紋理圖，N相……………....………70
圖25. compound C(n = 12)之光學紋理圖，SmC相……………...……..70
圖26. 相變化溫度與碳鏈長之柱狀圖………………..……………….72
圖27. 含雙金屬中心的錯化合物……………………………………...73
圖28. compound D結構圖……………………………………………..74
圖29. ESR圖……………………………………………………………74
圖30. compound E結構圖……………………………………………...76
圖31. 相變化溫度與碳鏈長之柱狀圖………………………………...77
圖32. 分子結構圖………………………………………………….......79
表目錄
表1. 桿狀液晶一般結構及常使用之官能基…………………………...6
表2. 實驗之化學藥品………………………………………..………...22
表3. 液晶相所具有之特殊光學紋理圖…………….…………………61
表4. compound A的DSC數據…………………….……………….…..63
表5. compound A元素分析理論與實驗值………….………………....66
表6. compound B的DSC數據………………………………………...67
表7. compound C的DSC數據………………………………………....71
表8. compound C元素分析理論與實驗值………………………….…73
表9. 含diketone之配位基的DSC相變化數據…………………….…75
表10. 為接銅錯合物(compound D)的DSC數據……………………..75
表11. 為diketone的DSC數據………………………………………...76
表12. compound E的DSC數據……………………………………......77
附圖目錄
附圖1. Methyl-4-Hexadectyloxybenzoate 之 1H-NMR圖譜……....1
附圖2. 4-Hexadectyloxybenzyl alcohol之 1H-NMR圖譜……….....2
附圖3. 4-Hexadectyloxybenzylacetonephone之 1H-NMR圖譜........3
附圖4. 4-Hexadectyloxybenzylacetonephone之 13C-NMR圖譜…...4
附圖5. Ethyl 4-ferrocenylbenzoate之 1H-NMR圖譜……...............5
附圖6. Ethyl 4-ferrocenylbenzoate之 13C-NMR圖譜……..............6
附圖7. 1-[4-(4-Hexadectyloxybenzyloxy)phenyl]-3-(4- ferrocenylphenyl)propane-1,3-dione之 1H-NMR圖譜....7
附圖8. 1-[4-(4-Hexadectyloxybenzyloxy)phenyl]-3-(4- ferrocenylphenyl)propane-1,3-dione之 13C-NMR圖譜...8
附圖9. 5-[4-(4-Hexadectyloxybenzyloxy)phenyl]-3-(4- ferrocenylphenyl)-1H-pyrazole之 1H-NMR圖譜……......9
附圖10. 5-[4-(4-Hexadectyloxybenzyloxy)phenyl]-3-(4- ferrocenylphenyl)-1H-pyrazole之13C-NMR圖譜…….....10
附圖11. 1-[4-(4-Dodectyloxybenzyloxy)phenyl]-3- phenylpropane-1,3-dione之1H-NMR圖譜……..................11
附圖12. 1-[4-(4-Dodectyloxybenzyloxy)phenyl]-3-phenyl propane-1,3-dione之13C-NMR圖譜…….............................12
附圖13. 5-[4-(4-Dodectyloxybenzyloxy)phenyl]-3-phenyl-1H- pyrazole之1H-NMR圖譜……................................................13
附圖14. 5-[4-(4-Dodectyloxybenzyloxy)phenyl]-3-phenyl-1H- pyrazole之13C-NMR圖譜……...............................................14
附圖15. 4-Dodectyloxyacetophenones之 1H-NMR圖譜……...........15
附圖16. (4-ferrocenylphenyl)methanol之 1H-NMR圖譜…….........16
附圖17. (4-ferrocenylphenyl)methanol之 13C-NMR圖譜……........17
附圖18. 4-(4-ferrocenylbenzyloxy)benzoic acid methyl ester
之 1H-NMR圖譜……...............................................................18
附圖19. 4-(4-ferrocenylbenzyloxy)benzoic acid methyl ester之 13C-NMR圖譜……..............................................................19
附圖20. 1-[4-(4-ferrocenylbenzyloxy)phenyl]-3-(4-dodectyl oxyphenyl)propane1,3dione之1H-NMR圖譜……..............20
附圖21. 1-[4-(4-ferrocenylbenzyloxy)phenyl]-3-(4-dodectyl oxyphenyl)propane1,3dione之13C-NMR圖譜…….............21
附圖22. 3-[4-(4-ferrocenylbenzyloxy)phenyl]-5- (4-dectyloxyphenyl)-1H-pyrazole之1H-NMR圖譜……..22
附圖23. 3-[4-(4-ferrocenylbenzyloxy)phenyl]-5- (4-dodectyloxyphenyl)-1H-pyrazole之13C-NMR圖譜….23
附圖24. 1-[4(4-Tetradecyloxybenzyloxy)phenyl]-3-[4- (4-ferrocenylphenyl)propane-1,3-dione 之1H-NMR圖譜……................................................................24
附圖25. 1-[4-(4-Tetradecyloxybenzyloxy)phenyl]-3-[4-(4- ferrocenylphenyl)propane-1,3-dione之13C-NMR圖譜...25
附圖26. 5-[4-(4-Tetradecyloxybenzyloxy)phenyl]-3-[4-(4- ferrocenylbenzyloxy)phenyl]-1H-pyrazole 之1H-NMR圖譜……................................................................26
附圖27. 5-[4-(4-Tetradecyloxybenzyloxy)phenyl]-3-[4- (4-ferrocenylbenzyloxy)phenyl]-1H-pyrazole 之13C-NMR圖譜……...............................................................27
附圖28. 5-[4-(4-Octcyloxybenzyloxy)phenyl]-3-(4- ferrocenyl phenyl)-1H-pyrazole之DSC圖譜……..............................28
附圖29. 5-[4-(4-Hexadecyloxybenzyloxy)phenyl]-3-(4- ferrocenylphenyl)-1H-pyrazole之DSC圖譜……...........29
附圖30. 5-[4-(4-Dodecyloxybenzyloxy)phenyl]-3-phenyl-1H- pyrazole之DSC圖譜….................................…....................30
附圖31. 3-[4-(4-Ferrocenylbenzyloxy)phenyl]-5(4- tetradecyloxyphenyl)-1H-pyrazole之DSC圖譜…….....31
附圖32. 1-[4-(4-Ferrocenylbenzyloxy)phenyl]-3-(4- tetradecyloxyphenyl)propane-1,3-dione之DSC圖譜...32
附圖33. Bis[1-[4-(4-ferrocenylbenzyloxy)phenyl]-3-(4- tetradecyloxyphenyl)propane-1,3-dione]copper(II) 之DSC圖譜…….....................................................................33
附圖34. 1-[4(4-Tetradecyloxybenzyloxy)phenyl]-3-[4-(4- ferrocenylbenzyloxy)phenyl]propane-1,3-dione 之DSC圖譜…….....................................................................34
附圖35. 5-[4-(4-Hexadecyloxybenzyloxy)phenyl]-3-[4-(4- ferrocenylbenzyloxy)phenyl]-1H-pyrazole 之DSC圖譜…….....................................................................35

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指導教授

賴重光(C. K. Lai)

審核日期

2003-7-16

推文