含氮氧原子之硼錯合物及雙同雜環分子之液晶性質探討

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：31

、訪客IP：18.119.103.40

姓名

蕭佩其(Pei-Chi Hsiao) 查詢紙本館藏

畢業系所

化學學系

論文名稱

含氮氧原子之硼錯合物及雙同雜環分子之液晶性質探討

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	★ 具有Quinoxaline結構之雙金屬無機液晶材料
★ 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

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)

在系列一中成功合成出以-enaminoketonates為配位基2ad，並與boron difluoride (BF2)形成錯合物1ad，其中1a及2a皆具有桿狀液晶的性質，藉由增加兩側烷氧鏈數目的化合物1bc及2bc則誘導出盤狀液晶相，而改變中心結構苯環為間位的化合物1d及2d並無液晶相的生成。並且由化合物1b (n = 8)單晶結構可得知，中心的硼原子為四面體，兩側苯環與配位結構環兩面角夾45.141，分子較不平面，且分子間的F-H氫鍵作用力過多，因此導致了化合物1b (n = 8)無液晶相的生成。化合物1ac的最大吸收波長及最大放光波長皆比化合物2ac紅位移，放光波長在溶液態λmax = 591644 nm而在固態時其放光在λmax = 604653 nm，在固態螢光光譜中化合物1a-c之放光波長皆比在溶液中紅位移，為J-aggregate現象發生。
第二系列成功合成出含有兩個pyrazole及isoxazole之對稱同雜環化合物3a-b，藉由引入雜環系統、改變分子軟硬端比及引入氫氧基來觀察以上因素對化合物液晶行為的影響，其中含pyrazole之化合物3a為桿狀液晶；而含isoxazole之化合物3b則不具有液晶性質。經由偏光紋理圖與powder X-ray diffraction實驗結果可判定，化合物4具有N相及SmC相，而含pyrazole之化合物3a則為SmA相。
第三系列成功合成出含有兩個pyrazole及1,3,4-oxadiazole之對稱同雜環化合物5a-b，藉由引入雜環系統及改變分子軟硬端比來觀察對化合物液晶行為的影響，此兩種化合物5a及5b皆為桿狀液晶。經由偏光紋理圖與powder X-ray diffraction實驗結果可判定，含pyrazole之化合物5a為SmA相，而化合物5b則具有N相及SmC相。化合物5b經240 nm波長的光激發後放出427 nm的紫光。

摘要(英)

In the first part, one new series of bis(boron difluoride) complexes 1ad derived from substituted -enaminoketonates 2ad were successfully synthesized, in which both 1a and 2a exhibit rod-like mesogen behavior. Increasing the number of terminal alkyl chains, compounds 1ac and 2ac exhibit columnar mesogen behaviour. Compounds 1d and 2d did not exhibit liquid crystal behaviour because of their bent stuctures. One single crystal and molecular structure of nonmesogenic BF2 complex 1b (n = 8) was resolved and the geometry of the central boron atom was tetrahedron. A larger dihedral angle of 45.141 between the phenyl rings and coordination structure ring observed in crystal lattice and excessive intermolecular hydrogen bonds were contributed to the lack of liquid crystallinity. The maximum absorption and the maximum luminescent emission of the compound 1ac were red-shifted compared to the compound 2ac. The luminescent emission of the compound 1ac in the solid state (λmax = 604653 nm) were red-shifted compared to in the solution (λmax = 591644 nm) because of the J-aggregate.
In the second part, a system of twin mesogens containing pyrazoles and isoxazoles was synthesized and characterized by 1H NMR, 13C NMR, Mass spectrometry and Elementary anaylysis. In this experiment, the effect of the above factors on the liquid crystal behavior of the compound was observed by introducing a heterocyclic system, changing the ratio of the hard and soft terminals and introducing a hydroxyl group. The results of POM and powder X-ray diffraction experiments indicate that the compound 4 exhibit SmC and N phase and the compound 3a exhibit SmA phase. Compound 3b did not exhibit liquid crystal behavior.
In the third part, a system of twin mesogens containing pyrazoles and 1,3,4-oxadiazoles was successfully synthesized. In this experiment, the effect of the above factors on the liquid crystal behavior of the compound was observed by introducing a heterocyclic system and changing the ratio of the hard and soft terminals. The results of POM and powder X-ray diffraction experiments indicate that the compound 5a exhibit SmA phase and the compound 5b exhibit SmC and N phase. Compound 5b emitted a pronounced violet emission at λmax = 427 nm in solution at room temperature

關鍵字(中)

★ 液晶

關鍵字(英)

論文目次

中文摘要 i
Abstract ii
謝誌 iv
第一章緒論 1
1-1 液晶簡介 2
1-2 液晶相形成條件 3
1-3 液晶相分類 5
1-3-1 向列型液晶 6
1-3-2 層列型液晶 6
1-3-3 盤狀液晶 7
1-4 Boron difluoride complex簡介 8
1-5 五圓雜環簡介 10
1-6 研究動機 12
1-6-1 系列一研究動機 13
1-6-2 系列二研究動機 15
1-6-3 系列三研究動機 16
第二章實驗部分 17
2-1 實驗藥品 18
2-2 儀器設備 20
2-3 實驗流程 22
2-3-1系列一之實驗流程 22
2-3-2系列二之實驗流程 24
2-3-3系列三之實驗流程 25
2-4實驗步驟 26
2-4-1系列一之合成 26
2-4-2系列二之合成 42
2-4-3系列三之合成 48
第三章結果與討論 54
3-1 系列一化合物之探討 55
3-1-1系列一之結構與代號 55
3-1-2系列一化合物1H NMR探討 56
3-1-3系列一化合物之偏光紋理圖 57
3-1-4系列一化合物之熱微差掃描分析儀(DSC) 60
3-1-5系列一化合物1b (n = 8)之單晶結構探討 65
3-1-6系列一化合物1a-1d之熱重量分析結果 70
3-1-7 系列一化合物之Powder X-ray 分析與分子模擬排列 71
3-1-8系列一化合物2a-2c及1a-1c光學性質探討 82
3-2 系列二化合物性質探討 84
3-2-1系列二之結構與代號 84
3-2-2系列二化合物之偏光紋理圖 85
3-2-3系列二化合物之熱微差掃描分析儀(DSC) 87
3-2-4系列二化合物3a-3b之熱重量分析結果 90
3-2-5系列二化合物之 Powder X-ray 分析與分子模擬排列 91
3-2-6系列二化合物3a及3b之紅外線光譜分析 94
3-2-7系列二化合物3a及3b光學性質探討 95
3-3 系列三化合物性質探討 96
3-3-1系列三之結構與代號 96
3-3-2系列三化合物之偏光紋理圖 97
3-3-3系列三化合物之熱微差掃描分析儀(DSC) 99
3-3-4系列三化合物5a-5b之熱重量分析結果 101
3-3-5系列三化合物之 Powder X-ray 分析與分子模擬排列 102
3-3-6系列三化合物5a及5b之紅外線光譜分析 106
3-3-7系列三化合物5a及5b光學性質探討 107
第四章結論 108
4-1 系列一結論 109
4-2 系列二結論 110
4-3 系列三結論 110
參考文獻 111
附圖 116
附表 156

參考文獻

1. P. J. Collings and M. Hird, 楊怡寬, 郭蘭生, 鄭殷立, 液晶化學及物理入門, 2001.
2. H. T. Nguyen, C. Destrade and J. Malthete, Adv. Mater., 1997, 9, 375388.
3. (a) C. Janiak, J. Chem. Soc., Dalton Trans., 2000, 38853896. (b) J. Liu, E. M. Murray and V. G. Young, Chem. Commun., 2003, 15, 19041905.
4. A. Grafe and D. Janietz, Chem. Mater., 2005, 17, 49794984.
5. C. R. Wen, Y. J. Wang and C. K. Lai, Chem. Mater., 2005, 17, 16461654.
6. E. J. Foster and C. Lavigueur, J. Mater. Chem., 2005, 15, 40624068.
7. F. Morale and R. W. Date, Chem. Eur. J., 2003, 9, 24842501.
8. T. L. Wu, M. J. Huang, C. C. Lin, P. Y. Huang, T. Y. Chou, R. W. C. Cheng, H. W. Lin, R. S. Liu and C. H. Cheng, Nature Photonics, 2018, 12, 235–240.
9. X. Li and Y. A. Son, Dyes Pigm., 2014, 107, 182–187.
10. C. Qian, M. Liu, G. Hong, P. Xue, P. Gong and R. Lu, Org. Biomol. Chem., 2015, 13, 2986–2998.
11. M. Santra, H. Moon, M. H. Park, T. W. Lee, Y. K. Kim and K. H. Ahn, Chem. Eur. J., 2012, 18, 9886–9893.
12. J. Massue, D. Frath, G. Ulrich, P. Retailleau and R. Ziessel, Org. Lett., 2012, 14, 230–233.
13. J. S. Lee, N. Y. Kang, Y. K. Kim, A. Samanta, S. Feng, H. K. Kim, M. Vendrell, J. H. Park and Y. T. Chang, J. Am. Chem. Soc., 2009, 131, 10077–10082.
14. G. Zhang, G. M. Palmer, M. W. Dewhirst and C. L. Fraser., Nat. Mater., 2009, 8, 747–751.
15. A. Ojida, T. Sakamoto, M. A. Inoue, S. H. Fujishima, G. Lippens and I. Hamachi, J. Am. Chem. Soc., 2009, 131, 6543–6548.
16. T. Kowada, H. Maeda and K. Kikuchi, Chem. Soc. Rev., 2015, 44, 4953–4972.
17. M. Chapran, E. Angioni, N. J. Findlay, B. Breig, V. Cherpak, P. Stakhira, T. Tuttle, D. Volyniuk, J. V. Grazulevicius, Y. A. Nastishin, O. D. Lavrentovich and P. J. Skabara, ACS Appl. Mater. Interfaces, 2017, 9, 4750−4757.
18. Q. Tang, W. Si, C. Huang, K. Ding, W. Huang, P. Chen, Q. Zhang and X. Dong, J. Mater. Chem. B, 2017, 5, 1566–1573.
19. D. O. Frimannsson, M. Grossi, J. Murtagh, F. Paradisi and D. F. O’Shea, J. Med. Chem., 2010, 53, 7337–7343.
20. A. D’Aléo and F. Fages, Photochem. Photobiol. Sci., 2013, 12, 500–510.
21. M. Mamiya, Y. Suwa, H. Okamoto and M. Yamaji, Photochem. Photobiol. Sci., 2016, 15, 928–936.
22. D. J. Wang, B. P. Xu, X. H. Wei and J. Zheng, J. Fluorine Chem., 2012, 140, 49–53.
23. K. Ono, K. Yoshikawa, Y. Tsuji, H. Yamaguchi, R. Uozumi, M. Tomura, K. Taga and K. Saito, Tetrahedron, 2007, 63, 9354–9358.
24. R. Yoshii, A. Nagai, K. Tanaka and Y. Chujo, Macromol. Rapid Commun., 2014, 35, 1315−1319.
25. R. S. Singh, M. Yadav, R. K. Gupta, R. Pandey and D. S. Pandey, Dalton Trans., 2013, 42, 1696–1707.
26. M. J. Kwak and Y. Kim, Bull. Korean Chem. Soc., 2009, 30, 2865–2866.
27. K. Benelhadj, J. Massue and G. Ulrich, New J. Chem., 2016, 40, 5877–5884.
28. Q. Liu, X. Wang, H. Yan, Y. Wu, Z. Li, S. Gong, P. Liu and Z. Liu, J. Mater. Chem. C, 2015, 3, 2953–2959.
29. T. M. H. Vuong, J. W. Aubatin, J. F. Lohier, N. Bar, S. Boudin, C. Labbé, F. Gourbilleau, H. Nguyen, T. T. Dang and D. Villemin, New J. Chem., 2016, 40, 6070–6076.
30. Y. Meesala, V. Kavala, H. C. Chang, T. S. Kuo, C. F. Yao and W. Z. Lee, Dalton Trans., 2015, 44, 1120–1129.
31. W. Li, W. Lin, J. Wang and X. Guan, Org. Lett., 2013, 15, 1768–1771.
32. H. M. Ko, J. Korean Chem. Soc., 2016, 60, 21−27.
33. S. M. Barbon, J. T. Price, P. A. Reinkeluers and J. B. Gilroy, Inorg. Chem., 2014, 53, 10585−10593.
34. X. Zhang, H. Yu and Y. Xiao, J. Org. Chem., 2012, 77, 669−673.
35. A. D′Aléo, A. Felouat, V. Heresanu, A. Ranguis, D. Chaudanson, A. Karapetyan, M. Giorgi and F. Fages, J. Mater. Chem. C, 2014, 2, 5208–5215.
36. E. C. Laage, J. F. Allem, O. Ruel, J. B. Baudin, V. Croquette, M. B. Desce, and L. Jullien, Chem. Eur. J., 2004, 10, 1445–1455.
37. L. A. Padilha, S. Webster, O. V. Przhonska, H. Hu, D. Peceli, T. R. Ensley, M. V. Bondar, A. O. Gerasov, Y. P. Kovtun, M. P. Shandura, A. D. Kachkovski, D. J. Hagan and E. W. Van Stryland, J. Phys. Chem. A, 2010, 114, 6493–6501.
38. C. Ran, X. Xu, S. B. Raymond, B. J. Ferrara, K. Neal, B. J. Bacskai, Z. Medarova and A. Moore, J. Am. Chem. Soc., 2009, 131, 15257–15261.
39. M. J. Mayoral, P. Ovejero, M. Cano and G. Orellana, Dalton Trans., 2011, 40, 377–383.
40. A. Sakai, M. Tanaka, E. Ohta, Y. Yoshimoto, K. Mizuno and H. Ikeda, Tetrahedron Lett., 2012, 53, 4138–4141.
41. G. Zhang, J. Chen, S. J. Payne, S. E. Kooi, J. N. Demas and C. L. Fraser, J. Am. Chem. Soc., 2007, 129, 8942–8943.
42. Y. Sun, D. Rohde, Y. Liu, L. Wan, Y. Wang, W. Wu, C. Di, G. Yu and D. Zhu, J. Mater. Chem., 2006, 16, 4499–4503.
43. C. A. DeRosa, J. S. Kosicka, Z. Fan, H. C. Hendargo, D. H. Weitzel, G. M. Palmer and C. L. Fraser, Macromolecules, 2015, 48, 2967−2977.
44. R. Yoshii, A. Nagai, K. Tanaka and Y. Chujo, Chem. Eur. J., 2013, 19, 4506–4512.
45. R. Tan, Q. Lin, Y. Wen, S. Xiao, S. Wang, R. Zhang and T. Yi, CrystEngComm, 2015, 17, 66746680.
46. A. Loudet and K. Burgess, Chem. Rev., 2007, 107, 4891−4932.
47. N. Boens, V. Leen and W. Dehaen, Chem. Soc. Rev., 2012, 41, 1130–1172.
48. J. Bañuelos, F. L. Arbeloa, T. Arbeloa, V. Martinez and I. L. Arbeloa, Applied Science Innovations Pvt. Ltd. 2012.
49. J. H. Olivier, F. Camerel, G. Ulrich, J. Barberá and R. Ziessel, Chem. Eur. J., 2010, 16, 7134–7142.
50. F. Camerel, L. Bonardi, G. Ulrich, L. Charbonnière, B. Donnio, C. Bourgogne, D. Guillon, P. Retailleau and R. Ziessel, Chem. Mater., 2006, 18, 5009–5021.
51. F. Camerel, L. Bonardi, M. Schmutz and R. Ziessel, J. Am. Chem. Soc., 2006, 128, 4548–4549.
52. S. M. Barbon, V. N. Staroverov, P. D. Boyle and J. B. Gilroy, Dalton Trans., 2014, 43, 240–250.
53. M. C. Chang, A. Chantzis, D. Jacquemin and E. Otten, Dalton Trans., 2016, 45, 9477–9484.
54. S. M. Barbon, J. T. Price, U. Yogarajah and J. B. Gilroy, RSC Adv., 2015, 5, 56316–56324.
55. M. C. Chang and E. Otten, Chem. Commun., 2014, 50, 7431–7433.
56. S. M. Barbon, V. N. Staroverov and J. B. Gilroy, J. Org. Chem., 2015, 80, 5226−5235.
57. (a) C. Chien, C. J. Chen, H. S. Sheu, G. H. Lee and C. K. Lai, Tetrahedron, 2010, 66, 3583–3592. (b) S. Y. Li, C. J. Chen, P. Y. Lo, H. S. Sheu, G. H. Lee and C. K. Lai, Tetrahedron, 2010, 66, 6101–6112. (c) C. J. Cheng, I. W. Wang, H. S. Sheu, G. H. Lee and C. K. Lai, Tetrahedron, 2011, 67, 8120–8130.
58. B. Roy, N. De and K. C. Majumdar, Chemistry, 2012, 18, 1456014588.
59. A. Kamal, E. V. Bharathi, J. S. Reddy, M. J. Ramaiah, D. Dastagiri, M. K. Reddy, A.Viswanath, T. L. Reddy, T. B. Shaik, S. N. C. V. L. Pushpavalli and M. P. Bhadra, Eur J Med Chem., 2011, 46, 691703.
60. D. H. Brown and P. Styring, Liq. Cryst., 2003, 30, 2330.
61. U. M. Kauhanka and M. M. Kauhanka, Liq. Cryst., 2006, 33, 121127.
62. H. Gallardo, F. R. Bryk, A. A. Vieira, T. E. Frizon, G. Conte, B. S. Souza, J. Eccher, I. H. Bechtold, Liq. Cryst., 2009, 36, 839845.
63. H. M. Kuo, S. L. Tsai, G. H. Lee, H. S. Sheu, C. K. Lai, Tetrahedron., 2013, 69, 618626.
64. R. Iglesias, J. L. Serrano, T. Sierra, Liq. Cryst., 1997, 22, 37–46.
65. J. Barbera, R. Gimenez, J. L. Serrano, R. Alcala, B. Villacampa, J. Villalba, I. Ledoux, J. Zyss, Liq. Cryst., 1997, 22, 265273.
66. 雷子暘, 碩士論文, 中央大學化學研究所, 民國一百零七年.
67. 林彥君, 碩士論文, 中央大學化學研究所, 民國一百零二年.

指導教授

賴重光(Chung K. Lai)

審核日期

2019-7-6

推文