四銅酸酯及水楊醛與過渡金屬及二氟化硼錯合物之液晶性質探討

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：24

、訪客IP：18.119.28.184

姓名

池忻芸(Hsin-Yun Chih) 查詢紙本館藏

畢業系所

化學學系

論文名稱

四銅酸酯及水楊醛與過渡金屬及二氟化硼錯合物之液晶性質探討

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)

系列一，本研究以 tetraketonates 作為核心合成出化合物 1a-c, 1a-c BF2 及金屬錯合物 1b-M (M = Ni, Cu, Pd)。由實驗結果發現，化合物 1a-c 皆不具有液晶性質，而 1b-BF2 (n = 10, 12) 形成 Colr、1c-BF2 (n = 8, 10, 12) 及 1b-Cu (n = 12) 皆表現出筒狀液晶 Colh。化合物 1c-BF2 (n = 12) 為目前少見含雙 BF2 結構之盤狀室溫液晶，並於 BF2 配位後最大放光波長紅移，且螢光強度增強，化合物 1a-c BF2 之放光於溶液下均為黃色，其中 1c-BF2 (n = 12) max = 572 nm 為此系列放光波長最長之分子。
系列二，近幾年發光液晶同時結合發光特性和自組裝特性，吸引了眾多商業和學術研究關注。然而市售的染料液晶通常會因為聚集而導致猝滅 (aggregation-caused quenching, ACQ) 效應，使應用性受到限制。相反的聚集誘導放光 (aggregation-induced emission, AIE) 不僅改善了螢光焠滅的問題，還表現出良好的介晶性質; Salicylaldimine 常作為 AIE 材料之官能基，因此本研究合成一系列以 pyridine 為核心，且以 Salicylaldimine 作為連接基之發光液晶，由實驗結果發現，化合物 2a (n = 8, 10, 12) 為雙向液晶 SmA, SmC、2a-BF2 (n = 4-12) 皆表現出層狀液晶相。化合物於 BF2 配位後最大放光波長紅移，由 AIE 效應測試發現，當化合物 2a-BF2 (n = 12) 水含量 80 % 時，其放光強度最強 max = 524 nm，ΦF = 71.42 %。

摘要(英)

In the first series, columnar bis(BF2)2 complexes, containing tetraketonates as a central core with two β-diketonates incorporated, 1a-c, 1a-c BF2 and 1b-M (M = Ni, Cu, Pd) were prepared. All compounds were characterized by 1H and 13C NMR spectroscopy, and element analysis. Their mesomorphic and optical behavior was studied by polarizing microscope and differential scanning calorimetry and photofluorescence spectrometer. Their phase structures were confirmed by powder X-ray diffraction. Results showed that the derivatives 1a-c were nonmesogenic, while compounds 1b-BF2 (n = 10, 12), 1c-BF2 (n = 8, 10, 12) and 1b-Cu exhibited enantiotropic columnar mesophases. Compound 1c-BF2 (n = 12) was room temperature Colh liquid crystal. Compound 1b-BF2 (n = 8, 10, 12) formed Colr phase. The PL emissions of complexes 1a-c BF2 (n = 8, 10, 12) possess a pronounced green emission in solution. The PL emission of 1b-BF2 (n = 12) showed a strong dependence on structural moiety incorporated with max = 565 nm.

In the second series, a new of borondifluoride complexes 2a-BF2 derived from eneamines 2a were reported, and their mesomorphic and optical properties were also investigated. The optical property of the boron complexes was dependent on their molecular structures, The maximum absorption and the maximum luminescent emission of the compound 2a-BF2 were red-shifted compared to the compound 2a. The 2a-BF2 (n = 12) have the property of AIE (%v/v = 80% (THF/H2O)) , max = 524 nm, ΦF = 35.71 %), and it can be a protential material of luminescence in the future.

關鍵字(中)

★ 液晶
★ 盤狀液晶
★ 六角柱相
★ 矩形相
★ 二氟化硼
★ 縮合反應

關鍵字(英)

★ liquid crystal
★ columnar
★ hexagonal phases
★ rectangular phases
★ BF2 complexes
★ condensation reaction

論文目次

中文摘要 i
Abstract ii
謝誌 iii
第一章緒論 1
1-1 液晶簡介 2
1-2 液晶分子之基礎架構 3
1-3-1 桿狀液晶 8
1-3-2 盤狀液晶 9
1-4 無機液晶材料之特性 10
1-5 Boron difluoride complex 簡介 13
1-6 研究動機 15
1-6-1 系列一研究動機 15
1-6-2 系列二研究動機 17
第二章實驗部分 18
2-1 實驗藥品 19
2-2 儀器設備 21
2-3 實驗流程 25
2-3-1系列一之實驗流程 25
2-3-2系列二之實驗流程 25
2-4實驗步驟 27
2-4-1系列一之合成 27
2-4-2系列二之合成 40
第三章結果與討論 45
3-1系列一之結構與代號 46
3-1-1 系列一化合物之合成探討 47
3-1-2 系列一化合物 1H NMR 探討 49
3-1-3系列一化合物之偏光紋理圖 51
3-1-4系列一化合物之熱微差掃描分析儀(DSC) 55
3-1-5系列一化合物1a和1b之熱重量分析結果 59
3-1-6系列一化合物之 Powder X-ray 分析與分子模擬排列 61
3-1-7系列一化合物 1a-c 及 1a-c BF2 之光學性質探討 67
3-1-8化合物 1b-Cu 之 EPR 性質探討 69
3-2 系列二化合物性質探討 70
3-2-1 系列二之結構與代號 70
3-2-2系列二化合物1H NMR探討 71
3-1-3 系列二化合物之偏光紋理圖 (POM) 72
3-1-4系列二化合物之熱微差掃描分析儀 (DSC) 75
3-1-5系列二化合物之熱重量分析結果 77
3-1-7 系列二化合物之Powder X-ray 分析與分子模擬排列 79
3-1-8系列二化合物之光學性質探討 82
第四章結論 87
4-1 系列一結論 88
4-1 系列二結論 89
第五章曾製備過之結構 90
5-1系列一 91
5-1-1 系列一之 1H NMR, 19F NMR 探討 92
5-1-2 系列一之 POM 探討 93
5-2 系列二 94
5-3 系列三 95
5-3-1 系列三之 1H NMR, 19F NMR 探討 96
5-3-2 系列三之 POM 探討 97
5-4 系列四 98
5-4-1 系列四之 1H NMR, 19F NMR 圖譜 99
5-4-2 系列四之 POM 探討 100
5-5 系列五 101
5-5-1 系列五之 1H NMR 圖譜 101
5-6 系列六 102
5-6-1 系列六之 1H NMR 圖譜 102
5-6-2 系列六之 POM 探討 104
5-7 系列七 105
5-7-1 系列七之 1H NMR 圖譜 106
5-7-2 系列七之 POM 探討 106
參考文獻 108
附圖 113

參考文獻

1. P. J. Collings, 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. Eugene Kwan, Evans Group Seminar., 2009.
4. Richard P. Matthews, Tom Welton and Patricia A. Hunt, Phys. Chem. Chem. Phys., 2014, 16, 3238-3253.
5. Peter S. Pershan, Physics Today, 1982, 35,, 34-39.
6. C. R. Wen, Y. J. Wang and C. K. Lai, Chem. Mater., 2005, 17, 1646-1654.
7. E. J. Foster and C. Lavigueur, J. Mater. Chem., 2005, 15, 4062-4068.
8. F. Morale and R. W. Date, Chem. Eur. J., 2003, 9, 2484-2501.
9. H. Fischer; T. Plesnivy; M. Seitz, J. Mater. Chem. 1998, 8, 343-351.
10. T. Renouard; R. A. Fallahpour; M. Gratzel, Inorg. Chem. 2002, 41, 367-378.
11. U. Pietrasik; J. Szydłowska; A. Krówczyński, Chem. Mater., 2004, 16, 1485-1492.
12. M. Bose; K. Ohta; Y. Babu; M. D. Sastry, Chemical Physics Letters, 2000, 324, 330-336.
13. R. Tamura; Y. Uchida; N. Ikuma, J. Mater. Chem., 2008, 18, 2872-1876.
14. S. H. Simpson; R. M. Richardson; S. Hanna, Journal of Chemical Physics, 2007, 127, 104901.
15. C. Tan; B. M. Fung, Liq. Cryst., 2003, 30, 623-626.
16. G. Carbone; G. Lombardo; R. Barberi, Physical Review Letters, 2009, 103, 167801.
17. R. W. Date; E. F. Iglesias; D. W. Bruce, Dalton Trans., 2003, 1914-1931.
18. D. Pucci; G. Barberio; E. I. Szerb, Eur. J. Inorg. Chem., 2005, 12, 2457-2463.
19. A. Loudet and K. Burgess, Chem. Rev., 2007, 107, 4891-4932.
20. G. Ulrich , R. Ziessel and A. Harriman, Angew. Chem, 2008, 47, 1184-1201.
21. N. Boens , V. Leen and W. Dehaen, Chem. Soc. Rev., 2012, 41, 1130-1172.
22. A. Kamkaew , S. H. Lim , H. B. Lee , L. V. Kiew , L. Y. Chung and K. Burgess, Chem. Soc. Rev., 2013, 42, 77-88.
23. X. Li and Y. A. Son, Dyes Pigm., 2014, 107, 182-187.
24. C. Qian, M. Liu, G. Hong, P. Xue, P. Gong and R. Lu, Org. Biomol. Chem., 2015, 13, 2986-2998.
25. M. Santra, H. Moon, M. H. Park, T. W. Lee, Y. K. Kim and K. H. Ahn, Chem. Eur. J., 2012, 18, 9886-9893.
26. J. Massue, D. Frath, G. Ulrich, P. Retailleau and R. Ziessel, Org. Lett., 2012, 14, 230-233.
27. 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.
28. G. Zhang, G. M. Palmer, M. W. Dewhirst and C. L. Fraser., Nat. Mater., 2009, 8, 747-751.
29. A. Ojida, T. Sakamoto, M. A. Inoue, S. H. Fujishima, G. Lippens and I. Hamachi, J. Am. Chem. Soc., 2009, 131, 6543-6548.
30. T. Kowada, H. Maeda and K. Kikuchi, Chem. Soc. Rev., 2015, 44, 4953-4972.
31. 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.
32. 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.
33. D. O. Frimannsson, M. Grossi, J. Murtagh, F. Paradisi and D. F. O’Shea, J. Med. Chem., 2010, 53, 7337-7343.
34. A. D’Aléo and F. Fages, Photochem. Photobiol. Sci., 2013, 12, 500-510.
35. M. Mamiya, Y. Suwa, H. Okamoto and M. Yamaji, Photochem. Photobiol. Sci., 2016, 15, 928-936.
36. D. J. Wang, B. P. Xu, X. H. Wei and J. Zheng, J. Fluorine Chem., 2012, 140, 49-53.
37. K. Ono, K. Yoshikawa, Y. Tsuji, H. Yamaguchi, R. Uozumi, M. Tomura, K. Taga and K. Saito, Tetrahedron, 2007, 63, 9354-9358.
38. R. Yoshii, A. Nagai, K. Tanaka and Y. Chujo, Macromol. Rapid Commun., 2014, 35, 1315-1319.
39. R. S. Singh, M. Yadav, R. K. Gupta, R. Pandey and D. S. Pandey, Dalton Trans., 2013, 42, 1696-1707.
40. M. J. Kwak and Y. Kim, Bull. Korean Chem. Soc., 2009, 30, 2865-2866.
41. K. Benelhadj, J. Massue and G. Ulrich, New J. Chem., 2016, 40, 5877-5884.
42. 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.
43. 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.
44. Y. Meesala, V. Kavala, H. C. Chang, T. S. Kuo, C. F. Yao and W. Z. Lee, Dalton Trans., 2015, 44, 1120–1129.
45. W. Li, W. Lin, J. Wang and X. Guan, Org. Lett., 2013, 15, 1768–1771.
46. H. M. Ko, J. Korean Chem. Soc., 2016, 60, 21-27.
47. S. M. Barbon, J. T. Price, P. A. Reinkeluers and J. B. Gilroy, Inorg. Chem., 2014, 53, 10585-10593.
48. X. Zhang, H. Yu and Y. Xiao, J. Org. Chem., 2012, 77, 669-673.
49. 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.
50. 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.
51. 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.
52. 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.
53. M. J. Mayoral, P. Ovejero, M. Cano and G. Orellana, Dalton Trans., 2011, 40, 377-383.
54. A. Sakai, M. Tanaka, E. Ohta, Y. Yoshimoto, K. Mizuno and H. Ikeda, Tetrahedron Lett., 2012, 53, 4138-4141.
55. 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.
56. 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.
57. 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.
58. R. Yoshii, A. Nagai, K. Tanaka and Y. Chujo, Chem. Eur. J., 2013, 19, 4506-4512.
59. R. Tan, Q. Lin, Y. Wen, S. Xiao, S. Wang, R. Zhang and T. Yi, CrystEngComm, 2015, 17, 6674-6680.
60. A. Loudet and K. Burgess, Chem. Rev., 2007, 107, 4891-4932.
61. N. Boens, V. Leen and W. Dehaen, Chem. Soc. Rev., 2012, 41, 1130-1172.
62. Miriam Más-Montoya, María F. Montenegro, Arturo Espinosa Ferao, Alberto Tárraga, José Neptuno Rodríguez-López, and David Curiel, Organic Letters, 2020, 22, 3356-3360.
63. Ju Mei, Yuning Hong, Jacky W. Y. Lam, Anjun Qin, Youhong Tang and Ben Zhong Tang Adv. Mater. 2014, 26, 5429-5479.
64. Luyi Zong, Yujun Xie, Can Wang, Jian-Rong Li, Qianqian Li and Zhen Li, Chem. Commun., 2016, 52, 11496-11499.
65. 王國維, 碩士論文, 中央大學化學研究所, 民國 87 年
66. Hongbo Lu, Shanna Zhang Aixiang Ding, Miao Yuan, Guiyu Zhang, Wei Xu, Guobing Zhang, Xianghua Wang, Longzhen Qiu and Jiaxiang YangNew J. Chem., 2014, 38, 3429-3433.

指導教授

賴重光(Chung-Kung Lai)

審核日期

2021-7-20

推文