臺灣博碩士論文加值系統

摘要

我們合成了一系列Donar-acceptor具推拉電子的紫質非線性分子，紫質在D和A之間扮演著能提供強的電子偶合的橋基。有機分子若是具有強的電子推拉電子基以及大的π- 共軛系統的結構，都會表現出高的β值，所以這裡我們利用三鍵的乙炔基來擴大系統的π- 共軛性。這些樣品的製備是利用Sonogashira cross-coupling。

另外我們也合成一系列紫質染料應用於太陽能電池的研究。我們可以藉由觀測紫外-可見光光譜以及螢光光譜來探討紫質和perylene之間能量傳遞的關係。我們相信紫質- perylene系統在太陽能電池領域中，可以有不錯的表現。

Abstract

A series of zinc porphyrins with both electron donor and acceptor groups were synthesized for use as NLO chromophores in optoelectronic materials and devices.The porphyrin bridge connecting D and A groups should provide a pathway for strong electronic coupling between D and A. Organic molecules with strong electron donor and electron aceptor groups that are connected by a large conjugated π– electron system usually show high β values, so we utilized a ethynyl unit to extendπ– conjugation of the systems. The preparation of porphyrins with ethyne-linked functional groups can be achieved by the
sonogashira cross-coupling method.


Light - harvesting arrays that consist of porphyrin and perylene units were synthesized. These arrays show broad absorption in the visible region. The energy transfer between porphyrin and perylene pigments was investigated by fluorescence spectroscopy. We except that porphyrin – perylene systems have high energy conversion efficiency in
solar cells.

目錄
中文摘要----------------------------------------------------------------------------I
英文摘要---------------------------------------------------------------------------II
目錄--------------------------------------------------------------------------------III
圖目錄----------------------------------------------------------------------------V
第一章 緒論
1-1 紫質簡介…………………………………………………… 1
1-2光誘導電子轉移理論與分子導線………………………… 7
1-3 高共軛多紫質的簡介……………………………………… 12
第二章 紫質應用於非線性光學
2-1 緒論………………………………………………………… 15
2-2 研究動機與方向……………………………………………. 20
2-3 合成
2-3-1 紫質及其衍生物的合成……………………………… 21
2-3-2 紫質染料的合成……………………………………… 26
2-4 結果與討論
2-4-1 合成結果………………………………………………… 34
2-4-2 UV-vis光譜………………………………………… 36
2-5 結論…………………………………………………39
第三章 紫質應用於太陽能電池
3-1 緒論……………………………………………………… 40
3-2 研究動機與方向…………………………………………… 42
3-3 合成
3-3-1紫質衍生物與perylene之合成……………………… 43
3-3-2染料之合成……………………………………………… 45
3-4 結果與討論
3-4-1 UV-vis吸收光譜………………………………………… 48
3-4-2 螢光放射光譜…………………………………………… 50
3-5 結論………………………………………………………… 54
3-6 未來展望…………………………………………………… 55
第四章 實驗步驟
4-1 藥品與儀器………………………………………………… 57
4-2實驗步驟…………………………………………………… 60
參考資料 …………………………………………………….78
附錄…………………………………………………………...80

參考資料

1. Omura, T.; Sato, R. J. Biol. Chem. 1994, 239, 2370.
2. Dophin, D. Ed. The porphyrins, New York, 1978.
3. Anderson, H. L. Chem. Commun. 1999, 2323-2330.
4. Kadish, K. M.; Smith , K. M.; Gruilard, R. Eds. The porphyrin handbook 2000, Vol. 1.
5. Vollmer, M. S.; Würthner, F.; Effenberger, F. ; Emele, P.; Meyer, D. U.; Stümpfig, T.; Port, H.; Wolf, H. C. Chem. Eur. J. 1998, 4, 260 -269
6. Kawao, M.; Ozawa, H.; Tanaka, H.; Ogawa, T. Thin Solid Films. 2006, 499, 23 – 28
7.Imahori, D.; Tamaki, K.; Araki, Y.; Sekiguchi, Y.; Ito, O.; Sakata, Y.; Fukuzumi, S. J. Am. Chem. Soc. 2002, 124, 5165-5174
8.Zhang, T. G.; Zhao, Y.; Asselberghs, I.; Persoons, A.; Clays, K ; Therien, M. J. J. Am. Chem .Soc. 2005, 127, 9710-9720
9. Kadish, K. M.; Smith, K. M.; Gruilard,R. Eds. The porphyrin handbook 2000, 8, 156
10. Robertson, N; McGowan, C. A. Chem. Soc. Rev. 2003, 32, 96–103
11. Launay, J. P. Chem. Soc. Rev., 2001, 30, 386-397
12. Reimers, J. R.; Hall, L. E ; Crossley, M. J ; Hush , N. S. J. Phys. Chem. A 1999, 103, 4385-4397
13. Aratani, N.; Cho, H. S.; Ahn, T. K.; Cho, S.; Kim, D.; Sumi, H. ; Osuka, A. J. Am. Chem. Soc. 2003, 125, 9668-9681 14. Ogawa, K.; Zhang, T.; Yoshihara, K.; Kobuke, Y. J. Am. Chem. Soc. 2002, 124, 22-23
15. Sessler, J. L.; Wangt, B.; Harriman, A. J. Am. Chem. Soc. 1995,117, 704-714
16. Priyadarshy, S.;Therien, M. D.; Beratan, D. N. J. Am. Chem. Soc. 1996, 118, 1504-1510
17. Arnold, D. P.; Hartnell, R. D.; Heath, G.A.; Newbya, L.; Webster, R.D. Chem. Comm., 2002, 754–755
18. (a) Choi, M. S.; Yamazaki, T.; Yamazaki, I.; Aida, T. Angew. Chem. 2004, 43, 150 –158
(b) Yu, L.; Lindsey, J. S. Tetrahedron, 2001, 57, 9285-9298
19. Ambroise, A.; Wagner, R. W.; Rao, P. D.; Riggs, J. A.; Hascoat, P.; Diers, J. R.; Seth, J.; Lammi, R. K.; Bocian, D. F.; Holten, D.; Lindsey,J. S. Chem. Mater. 2001, 13, 1023-1034
20. Susumu, K.; Therien, M. J. J. Am. Chem. Soc. 2002, 124, 8550-8552, and references
21. Priyadarshy, S.; Therien, M. J.; Beratan, D. N. J. Am. Chem. Soc. 1996, 118, 1054.
22. LeCours, S. T.; Guan, H. W.; DiMagno, S. G.; Wang, C. H.; Therin, M. J. J. Am.
Chem. Soc. 1996, 118, 1497-1503.
23. Hasselman, G. M.; Watson, D. F.; Stromberg, J. R.; Bocian, D. F.; Holten, D.; Lindsey, J. S.; Meyer, G. J. J. Phys. Chem. B. 2006, 110, 25430-25440
24. Tomizaki, K. Y.; Loewe, R, S.; Kirmaier, C.; Schwartz, J. K.; Retsek, J. L.; Bocian, D. F.; Holten, D; Lindsey, J. S. J. Org. Chem. 2002, 67, 6519-6534
25. Ka, J. W.; Lee, C. H. Ttrahedron Letter, 2000, 41, 4609.
26. Plater, M. J.; Aiken, S.; Bourhill, G. Ttrahedron, 2002, 58, 2405
27. Plater, M. J.; Aiken, S.; Bourhill, G. Ttrahedron, 2002, 58, 2415
28. Li, F.;Yang, K.;Tyhonas, J. S.; Maccrum, K. A.;Lindsey, J. S. Ttrahedron, 1997, 53, 12339
29. Monnereau, C.;Blert, E.; Montembault, V.; Fontaine, L.; Odobel, F. Ttrahedron, 2005, 61, 10113
30. Susumu, K.; Frail, P. R.; Angiolillo, P. J.; Therien, M. J. J. Am. Chem. Soc. 2006, 128, 8380-8381, and references
31. Ray, P. C.; Bonifassi, P.; Leszczynski, J. J. Phys. Chem. A. 2008, 112, 2870- 2879
32. Tomizaki, K. Y; Thamyongkit, P.; Loewe, R. S.; Lindsey, J. S. Tetrahedron, 2003, 59, 1191-1207
33. Gosztola, D.; Niemczyk, M. P.; Wasielewski , M. R. J. Am. Chem. Soc. 1998, 120, 5118-5119, and reference