具有Quinoxaline結構之雙金屬無機液晶材料

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：37

、訪客IP：18.217.161.27

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

★ 具有benzoxazole結構之無機液晶材料	★ 以1,3,4-thiadiazole為架構之不對稱無機液晶材料
★ 新穎香蕉形液晶及對稱含萘環之液晶分子	★ 香蕉形無機液晶
★ 具有benzoxazole結構之有機及無機液晶材料	★ 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	★ 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

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

至系統瀏覽論文 ( 永不開放)

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
附圖…………………………………………………………………128

參考文獻

1. M. A. Reppy, D. L. Gin, D. H. Gray, B. A. Pindzola and J. L. Smithers, J. Am. Chem. Soc., 2001, 123, 363.
2. W. R. Li, J. C. Su, Y. C. Ke and C. K. Lai, J. Mater. Chem., 2001, 11, 1763.
3 R. J. Bushby, R. Abeysekera, C. Caillet, I. W. Hamley, O. R. Lozman, Z. Lu and A. W. Robards, Macromolecules, 2003, 36, 1526.
4. 松本正一, 角田市良合著, 劉瑞祥譯, 液晶之基礎與應用, 民國九十二年.
5. P. J. Collings and M. Hird, 楊怡寬, 郭蘭生, 鄭殷立編譯, 液晶化學及物理入門, 2001.
6. A. Fukuda, Y. Takanishi, T. Isozaki and K. Ishikawa, J. Mater. Chem., 1994, 4, 1997.
7. C. K. Lai, H. C. Wu, J. H. Sung and C. D. Yang, Liq. Cryst., 2001, 28, 411.
8. S. Kumar, S. K. Varshney, Organic letters, 2002, 4, 157.
9. Adam Tracz, Jeremiasz K. Jeszka, J. Am. Chem. Soc., 2003, 125, 1682.
10. Shengxiong Xiao, Matthew Myers, Qian Miao, S_bastien Sanaur, Keliang Pang, Michael L. Steigerwald, and Colin Nuckolls, Angew. Chem. Int. Ed. 2005, 44, 2–6
11. Ming-Hui Qi and Guo-Fa Liu, J. Mater. Chem., 2003, 13, 2479.
12. Vladimir B. Bojinov and Ivo K. Grabchev, Org. Lett., Vol. 5, No. 12,2185.
13. Xuelong Zhang, Hideki Gorohmaru, Masami Kadowaki, Takako Kobayashi, Tsutomu Ishi-i, Thies Thiemanna and Shuntaro Mataka, J. Mater. Chem . , 2004,14,1901
14. Ivo Grabchev, Ivanka Moneva, Vladimir Bojinovb and Sylvie Guittonneau, J. Mater. Chem., 2000, 10, 1291.
15. T. Hirose, K. Tsuya, T. Nishigaki, Liq. Crystals., 1989, 4, 653.
16. Jens Barche, Silvia Janietz, Chem. Mater., 2004, 16, 4286.
17. Denis Haristoy, Dimitris Tsiourvas, Chem. Mater., 2003, 15, 2079.
18 Torsten Hegmann, Bernhard Neumann, J. Mater. Chem., 2005, 15, 1025.
19. Chang-Rong Wen, Chung K. Lai, Chem. Mater., 2005, 17, 1646.
20. Theo J. Dingemans, N. Sanjeeva Murthy, J. Phys. Chem. B, 2001, 105, 8845
21. J. Barbera´ , R. Gime´nez, M. Marcos, J. L. Serrano, P.J. Alonso, and J. I. Martı´nez Chem. Mater. 2003, 15, 958-964
22. Reinhard Paschke, Stefan Liebsch, Carsten Tschierske, Michael A. Oakley, and Ekkehard Sinn,Inorg. Chem. 2003, 42, 8230-8240
23. A. I. Pavluchenko, N. I. Smirnova, K. M. Djumaev, Mol. Cryst. Liq.
Cryst. 1976, 37, 35.
24. U. Caruso, R. Centore, A. Roviello, A. Sirigu, Macromolecules,
1992, 25, 2290.
25. Prog. Polym. Sci. 28 (2003) 1049–1105
26. Ioan Paraschiv, Marcel Giesbers, Barend van Lagen, Ferdinand C.Grozema, Ruben D. Abellon, Laurens D. A. Siebbeles, Antonius T. M. Marcelis, Han Zuilhof, and Ernst J. R. Sudho¨lter. Chem. Mater.; 2006; 18(4); 968-974
27. S. SAKAGAMI, T. KOGA, M. NAKAMIZO and A. TAKASE, Liquid Crystals, 2001, 28, 347- 350
28. Otto’ Berkesi, Tama’s Kortve’ lyesi, Csaba Hete’nyi, Tama’s Ne’meth and Istva’n Pa’linko, Phys. Chem. Chem. Phys., 2003, 5, 2009–2014
29. Toshio Kawasaki, Toshihide Kamata, Hirobumi Ushijima, Mitsuhiro Kanakubo, Shigeo Murata, Fujio Mizukami, Yuki Fujii and Yoshiharu Usui , J. Chem. Soc., Perkin Trans. 2, 1999, 193–198
30. Michael Kasha, Jozef Heldt, and David Gormin, J. Phys. Chem. 1995,99, 7281-7284
31. Aysegul Golcu , Mehmet Tumer , Havva Demirelli , R. Alan Wheatley,Inorganica Chimica Acta, 358,(2005) ,1785–1797
32. G. C. PERCY, D. A. THORNTON, J. inorg, nucl. Chem., 1972, 34, 3357-3367.
33. 梁文傑,CHEMISTRY（THE CHINESE CHEM. SOC., TAIPEI）March. 2004, 62, 43~58
34. Takakazu Yamamoto, Kiyoshi Sugiyama, Takashi Kushida, Tetsuji Inoue, andTakaki Kanbara, J. Am. Chem. Soc. 1996, 118, 3930-3937
35. CHUNG K. LAI, HO-CHIH LIU , FU-JOUN LI , KUNG-LUNG CHENG and HWO-SHUENN SHEU, Liquid Crystals, 32, 2005, 85–94
36. Nobuto Otsubo , Chie Okabe, Hirotoshi Mori , Kenji Sakota ,Kiichi Amimoto, Toshio Kawato , Hiroshi Sekiya, Journal of Photochemistry and Photobiology A: Chemistry 154 (2002) 33–39
37. Walter M. F. Fabian, Liudmil Antonov, Daniela Nedeltcheva, Fadhil S. Kamounah, and Peter J. Taylor, J. Phys. Chem. A 2004, 108, 7603-7612
38. Ralph S. Becker, Christian Lenoble, and Abudi Zein, J. Phys. Chem. 1987, 91, 3509-351

指導教授

賴重光(Chung-Kung Lai)

審核日期

2006-7-14

推文