| 姓名 |
胡惠美(Hui-Mei Hu)
查詢紙本館藏 |
畢業系所 |
化學學系 |
| 論文名稱 |
有機盤狀液晶分子之設計與合成
(organic discotic liquid crystal)
|
| 相關論文 | |
| 檔案 |
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| 摘要(中) |
II
中文摘要
系列一：合成出一系列bis-(1,3,4-oxadiazoles)的有機液晶分
子。所得之化合物經由1H- 和13C-NMR 光譜及元素分析(EA)加以鑑定
及結構與純度。而液晶現象的觀察，藉由熱差式掃瞄卡計儀(DSC)和
偏光顯微鏡(POM)來判斷。實驗結果顯示，不論其為meta 位置或para
位置之化合物，當側鏈基數目為6 時，均為Colh液晶相。然而meta
位置之化合物，當側鏈基碳數為8 至16 都是Colh液晶相，且液晶相
溫度範圍較寬廣，流動性也較佳。除了研究液晶相關性質，也做了一
些其他物性之探討。
系列二：合成一系列salicylaldimine 之配位基，此配位基在與
金屬(Pd、Cu)配位，形成錯合物。實驗結果得知，側鏈取代基為拉電
子基且接近苯環，會使液晶相溫度範圍縮短。進而發現，改變中心硬
段部分而合成benzoxazole 之錯合物，當側鏈基含有萘環時，其具有
N 液晶相。 |
| 摘要(英) |
In this work two series of heterocyclic compounds in which two
unsaturated five-membered ring based on 1,3,4-oxadiazole utilized as the
core center were generated and their mesomorphic properties investigated.
Some of this type of oxadiazole-based materials have been studied and
found to show novel properties, and these physical studies were focused
on electron-transporting capability or photoconducting for advanced
electronic devices. However, examples of mesomorphic 1,3,4-oxadiazole
derivatives were relatively scarce. 1,3,4-oxadiazole derivatives were
though considered as one of non-linear mesogenic compounds. Here we
report the first example derived from bis(1,3,4-oxadiazole) that exhibit a
columnar phase. Results indicated that all derivatives of 1,4-bis[2-(3,4,5
-trialkoxylphenyl)-1,3,4-oxadiazol-5-yl]benzenes and 1,3-bis[2-(3,4,5
-trialkoxylphenyl)-1,3,4-oxadiazol-5-yl]benzenes were columnar
mesophases. |
| 關鍵字(中) |
★ 盤狀液晶 |
關鍵字(英) |
★ discotic liquid crystal |
| 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....................................2
1-3 液晶分子結構之設計..................................3
1-4 液晶之種類..........................................4
1-5 液晶之性質..........................................9
1-6 無機液晶之特性......................................11
1-7 盤狀液晶之應用......................................14
1-8 研究動機............................................16
第二章實驗部分.........................................18
2-1 實驗藥品............................................19
2-2 儀器設備與方法......................................21
2-3 實驗流程............................................24
2-4 實驗步驟............................................28
2-4-1-1 Methyl-3,4,5-trialkoxybenzoates 之合成...........28
2-4-1-2 3,4,5-Trialkoxybenzoic acid 之合成...............30
2-4-1-3 3,4,5-Trialkoxybenzoic acid hydrazides 之合成....32
V
2-4-1-4 N,N-Bis（3,4,5-trialkoxybenzoyl）isophthaloyl acid
dihydrazides 之合成..............................34
2-4-1-5 N,N-Bis(3,4,5-trialkoxybenzoyl) terephthaloyl acid
dihydrazides 之合成..............................36
2-4-1-6 1,3-Bis[2-(3,4,5-trialkoxyphenyl)-1,3,4-oxadiazole
-5-yl]benzenes 之合成............................38
2-4-1-7 1,4-Bis[2-(3,4,5-trialkoxyphenyl)-1,3,4-oxadiazole
-5-yl]benzenes 之合成............................41
2-4-1-8 1,3-Bis[2-(3,4,5-trialkoxyphenyl)-1,3,4
-thiadiazole-5-yl]benzenes 之合成................43
2-4-2-1 4-Dodecyloxynitrobenzene 之合成..................46
2-4-2-2 4-Dodecyloxyphenylamine 之合成...................46
2-4-2-3 5-(2-Ethoxy-ethoxy)-2-hydroxymethylphenol 之合成
................................................47
2-4-2-4 4-Fluoro-2-hydroxybenzaldehyde 之合成............48
2-4-2-5 4-Chloro-2-hydroxybenzaldehyde 之合成............49
2-4-2-6 6-Octyloxy-naphthalene-2-carboxylic acid 之合成..49
2-4-2-7 6-Octyloxy-naphthalene-2-carboxylic acid 3-hydroxy-
4-(2-methoxy-ethyl)-phenyl ester 之合成..........50
2-4-2-8 2-[(4-Dodecyloxyphenylimino)methyl]-5-(2-ethoxy
-ethoxy)phenol 之合成............................51
2-4-2-9 2-[(4-Dodecyloxyphenylimino)methyl]-5-(2-ethoxy
-ethoxy)phenol palladium(Ⅱ)之合成..............56
2-4-2-10 2-[(4-Dodecyloxyphenylimino)methyl]-5-(2-ethoxy
-ethoxy)phenol copper(Ⅱ)之合成................58
VI
第三章結果與討論.......................................62
3-1-1 系列一化合物合成之反應機構探討..................63
3-1-2 FAB-MS 結果......................................65
3-1-3 液晶之鑑定......................................67
3-1-4 其他性質之探討..................................73
3-2-1 系列二化合物合成之反應機構探討..................81
3-2-2 液晶之鑑定......................................82
3-2-3 元素分析（EA）..................................88
3-2-4 ESR.............................................89
3-3 結論............................................91
參考資料.................................................92
VII
圖目錄
圖1.液晶分子設計之基本架構...............................3
圖2.液相型液晶之聚集方式.................................5
圖3.熱相型液晶之形成方式.................................5
圖4.盤狀液晶分子之排列...................................9
圖5.Bis-(1,3,4-oxadiazole)有機液子.......................16
圖6. Chem. Mater. 2001, 13, 1167-1173. OLED 材料之分子結構......17
圖7.系列一之bis-(1,3,4-oxadiazoles)之結構............... 17
圖8.系列二之salicylaldimine 錯合物之結構.................17
圖9.Bis-(1,3,4-oxadiazoles)之合環反應機構................63
圖10. Bis-(1,3,4-thiadiazoles)之合環反應機構.............64
圖11.化合物2a(n = 12)之FAB-MS 質譜圖.....................66
圖12.化合物3(n = 12)之FAB-MS 質譜圖......................66
圖13.化合物2a 的相變化柱狀圖.............................68
圖14.不同數目之側鏈取代基化合物的相變化柱狀圖............69
圖15.含不同元素(O、S)之化合物的相變化柱狀圖..............69
圖16.化合物3 的相變化柱狀圖..............................71
圖17.化合物2a（n = 12）在液晶相(85 ℃,100X)時的偏光紋理圖..72
圖18.化合物3（n = 12）在液晶相(80 ℃,100X)時的偏光紋理圖...72
圖19.化合物2a 之熱重分析圖...............................73
圖20.化合物3 之熱重分析圖................................74
圖21.化合物2a 吸收光譜圖.................................75
圖22.化合物3 吸收光譜圖..................................75
圖23.化合物2a 與化合物3 吸收光譜圖.......................76
圖24.化合物2a 與化合物3 螢光放射光譜圖...................77
VIII
圖25.化合物1 與化合物2a 螢光放射光譜圖...................78
圖26.化合物2a（n = 4）的CV 圖..............................79
圖27.Ortho-formylation of phenols 之反應機構..............81
圖28.側鏈基含氧之Pd 錯合物的相變化柱狀圖.................83
圖29.側鏈基含氧之Cu 錯合物的相變化柱狀圖.................84
圖30.鹵素取代基之Pd 錯合物的相變化柱狀圖.................86
圖31.鹵素取代基之Cu 錯合物的相變化柱狀圖.................86
圖32.側鏈基含萘環之錯合物的相變化柱狀圖..................88
圖33.側鏈基含氧之Pd 錯合物的ESR 圖.......................89
圖34.側鏈基含氧之Cu 錯合物的ESR 圖.......................89
圖35. Pd 錯合物(2a)在液晶相(196 ℃,100X)時偏光紋理圖......90
圖36. Cu 錯合物(2b)在液晶相(150 ℃,100X)時偏光紋理圖......90
IX
表目錄
表1.實驗所用之化學藥品...................................19
表2.系列一化合物之DSC 數據整理表.........................65
表3.化合物3 之DSC 數據整理表.............................68
表4.系列一化合物之螢光量子產率整理表.....................76
表5.化合物2a（n = 4）光學與電化學之特性....................78
表6.系列二側鏈基含氧之化合物DSC 數據整理表...............80
表7.側鏈為鹵素取代基之化合物DSC 數據整理表...............83
表8.側鏈基含萘環之化合物DSC 數據整理表...................85
表9.側鏈基含氧之化合物的元素分析.........................86
X
附圖目錄
附圖1. 3,4,5-Trialkoxybenzoic acid hydrazides 之1H NMR 圖譜..1
附圖2. N,N’-Bis(3,4,5-tridodecanoxybenzoyl)isophthaloyl acid
dihydrazide 之1H NMR 圖譜............................2
附圖3. N,N’-Bis(3,4,5-tridodecanoxybenzoyl)terephthaloyl
acid dihydrazide 之1H NMR 圖譜......................3
附圖4. 1,3-Bis[2-(3,4,5-tridodecanoxyphenyl)-1,3,4
-oxadiazol-5-yl]benzenes 之1H NMR 圖................4
附圖5. 1,3-Bis[2-(3,4,5-tridodecanoxyphenyl)-1,3,4
-oxadiazol-5-yl]benzenes 之13C NMR 圖譜.............5
附圖6. 1,4-Bis[2-(3,4,5-tridodecanoxyphenyl)-1,3,4
-oxadiazol-5-yl]benzenes 之1H NMR 圖譜..............6
附圖7. 1,4-Bis[2-(3,4,5-tridodecanoxyphenyl)-1,3,4
-oxadiazol-5-yl]benzenes 之13C NMR 圖譜.............7
附圖8. 1,3-Bis[2-(3,4,5-tridodecanoxyphenyl)-1,3,4
-thiadiazol-5-yl]benzenes 之1H NMR 圖譜.............8
附圖9. 1,3-Bis[2-(3,4,5-tridodecanoxyphenyl)-1,3,4
-thiadiazol-5-yl]benzenes 之13C NMR 圖譜............9
附圖10. 1,3-Bis[2-(3,4,5-tridodecanoxyphenyl)-1,3,4
-oxadiazol-5-yl]benzenes 之DSC 圖譜.............. 10
附圖11. 1,4-Bis[2-(3,4,5-tridodecanoxyphenyl)-1,3,4
-oxadiazol-5-yl]benzenes 之DSC 圖譜..............11
附圖12. 2-[(4-Dodecyloxyphenylimino)methyl]-5-(2-ethoxy
-ethoxy)phenol 之1H NMR 圖譜......................12
XI
附圖13. 2-[(4-Dodecyloxyphenylimino)methyl]-5-(2-ethoxy
-ethoxy)-phenol 之13C NMR 圖譜.....................13
附圖14. 6-Octyloxy-naphthalene-2-carboxylic acid 4-[(4
-dodecyloxyphenylimino)methyl]-3-hydroxy-phenyl
ester 之1H NMR 圖譜...............................14
附圖15. 6-Octyloxy-naphthalene-2-carboxylic acid 4-[(4
-dodecyloxyphenylimino)methyl]-3-hydroxy-phenyl
ester 之13C NMR 圖譜..............................15
附圖16. 6-Octyloxy-naphthalene-2-carboxylic acid 4-[(4
-dodecyloxy-2-hydroxy-phenylimino)methyl]-3-hydroxy
-phenyl ester 之1H NMR 圖譜.......................16
附圖17. 6-Octyloxy-naphthalene-2-carboxylic acid 4-[(4
-dodecyloxy-2-hydroxy-phenylimino)methyl]-3-hydroxy
-phenyl ester 之13C NMR 圖譜....................... 17
附圖18. 6-Octyloxy-naphthalene-2-carboxylic acid 4-(6
-dodecyloxy-benzoxazol-2-yl)-3-hydroxy-phenyl ester
之1H NMR 圖譜.....................................18
附圖19. 6-Octyloxy-naphthalene-2-carboxylic acid 4-(6
-dodecyloxy-benzoxazol-2-yl)-3-hydroxy-phenyl ester
之13C NMR 圖譜.....................................19
附圖20. 2-[(4-Dodecyloxyphenylimino)methyl]-5-(2-ethoxy
-ethoxy)phenol palladium(II)之DSC 圖譜...........20
附圖21. 2-[(4-Dodecyloxyphenylimino)methyl]-5-(2-ethoxy
-ethoxy)phenol copper(II)之DSC 圖譜..............21 |
| 參考文獻 |
參考資料
1. M. R. Bryce, Chem. Mater. 2001, 13, 1168.
2. N. Tamoto, C. Adachi, Chem. Mater. 1997, 9, 1079.
3. W. Dehaen, J. Org. Chem. 2001, 66, 4062.
4. C. Wang, M. R. Bryce, J. Mater. Chem. 2002, 12, 174.
5. M. Parra, J. Alderete, Liq. Cryst. 2002, 29, 1376.
6. D. Acierno, S. Concilio, Liq. Cryst. 2002, 29, 1387.
7. S. Y. Park, B. G. Kim, Tetrahedron Lett. 2001, 42, 2698.
8. P. Strohriegl, M. Greczmiel, Macromolecules. 1997, 30, 6045.
9. Z. Zheng, G. E. Jabbour, J. Am. Chem. Soc. 2001, 123, 6179.
10. Y. Xu, Z. Xu, B. Li, Liq. Cryst. 2002, 29, 199.
11. C. T. Chen, L.-H. Chan, Adv. Mater. 2001, 13, 1638.
12. C. K. Lai, C. R. Wen, Liq. Cryst. 2002, 29, 917.
13. D. Levin, R. Johnston, J. Chem. Soc., Perkin Trans. 1994,
1827.
14. N. U. Hofslokken, L. Skattebol, Acta Chem. Scand. 1999,
53, 258-260.
15. U. Caruso, A. Roviello, Liq. Cryst. 1988, 3, 1522.
16. A. Roviello, A. Sirigu, Liq. Cryst. 1988, 3, 121. |
| 指導教授 |
賴重光(CK Lai)
|
審核日期 |
2003-7-8 |
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