| 研究生: |
陳亮年 Liang-Nien Chen |
|---|---|
| 論文名稱: |
新型含二氮雜啡聚三烷基噻吩衍生物及其金屬錯合物的合成與光學性質的探討 |
| 指導教授: |
吳春桂
Chun-Guey Wu |
| 口試委員: | |
| 學位類別: |
碩士 Master |
| 系所名稱: |
理學院 - 化學學系 Department of Chemistry |
| 畢業學年度: | 93 |
| 語文別: | 中文 |
| 論文頁數: | 141 |
| 中文關鍵詞: | 二氮雜啡 、金屬錯合物 |
| 外文關鍵詞: | metal complex, phenanthroline |
| 相關次數: | 點閱:9 下載:0 |
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摘要
共軛高分子因其應用的多元性成為學界與業界的主要研究材料,就其應用在發光元件及化學感應器而言,含有-C=N- ( imine ) 結構的共軛高分子漸受重視。此類高分子除了具有一般有機物可合成出各種衍生物的特性外;其-C=N-官能基更能與多種的離子或化合物反應而改變光、電特性,因此可做為化學感應器;更有趣的是其可藉由和可發磷光的金屬形成錯合物,來提高量子產率與調變光色。本研究利用Yamamoto與Stille coupling合成出一系列具有 -C=N- 結構的聚三烷基噻吩衍生物Poly-3,8-n(4-octylthiophene-2,5-yl)-[1,10]-phenan -throline (n = bis, tetrakis ) 及其與 Cis-dichloro-bis ( 2,2’- bipyridine) ruthenium反應所做成的共軛分子-金屬錯合物。並以1H-NMR、FT-IR、MALDI-TOF、EA、GPC、TGA、UV-Vis、PL及TR-PL進行結構分析與物性測試。當高分子或其相對的單體與不同離子作用時,會有不同的光學特性變化,顯示其做為離子感應器的潛能,此外含phenanthroline的共軛分子或高分子與Ru反應所得的金屬錯合物的確可經由MLCT來調變光色,其中含Ru的Poly-3,8-bis(4-octylthioph- ene-2,5-yl)-[1,10]phenanthroline在CHCl3中的光色為非常漂亮的紅色。
Abstract
Conjugated polymer have become one type of the most interesting materials for both academia and industry, due to their widely applications. For applying in light-emitting device and chemical sensor, polymers structure containing the -C=N-( imine ) group has been noticed recently. Imine group in conjugated polymers not only has the characteristic of being a functional group for preparing derivatives but also reacts with various ions or molecules to alter the photophysics and electric properties of the polymers. Furthermore, the imine group can chelate with a phosphorescent metal to enhance the quantum yield of the polymer and at the same time tune the luminescence color. A novel series of conjugated polymers comprising -C=N- group: Poly-3,8-n(4-octylthiophene-2,5-yl)-[1,10]-phenanthroline (n = bis, tetrakis) and their ruthenium complexes which also contains cis-dichloro and bis ( 2,2’- bipyridine) ligands were synthesized using Yamamoto coupling and Stille coupling. They are characterized by 1H-NMR, FT-IR, MALDI-TOF, EA, GPC, TGA, UV-vis, PL and TR-PL. It was shown that the optical properties of the imine containing monomers and polymers change when their react with varions ions, showing a great potential for application in chemical sensors. The luminescence color of the phenanthroline containing polymers has change via a MLCT (metal to ligand charge transfer) mechanism when they reacted with ruthenium complexes. Poly-3,8-bis(4-octylthiophene-2,5-yl)-[1,10] phenanthroline is a blue emitter, whereas it emits a beautiful red light in CHCl3 solution when it was chelated with a ruthenium complexes.
參考文獻
1. Chiang, C. K.; Fincher, C. R.; Park, Y. W.; Heeger, A. J.; Shirakawa, H.; Louis, E. J.; Gau, S. C.; MacDiarmid, A. G. Phys. Rev. Lett. 1977, 39, 1098–1101.
2. Chien, J. C. W. “Polyacetylene:Chemistry, Physics, and Material Science”, Academic Press, Orlando, 1984.
3. Gazz, A. A. Chim. Ital. 1916, 46, Ⅱ279.
4. http://webpages.charter.net/dmarin/coat/#Conc
5. Dall, Olio A.; Dascola, G.; Varacca, V.;Bocchi, V. Acad. Sci. Ser. 1968, 433, C267.
6. Chen, T.-A.;Wu, X.; Rieke, R. D. J. Am. Chem. Soc. 1995, 117, 233-244.
7. Burroughes, J. H.;Bradley, D. D. C.;Brown, A. R.;Marks, R. N.;Mackay, K.;Friend, R. H.;Burns, P. L.;Holmes, A. B. Nature 1990, 347, 539-541.
8. Braun, D.;Heeger, A. J. Appl. Phys. Lett. 1990, 58, 1982-1984.
9. Susan, K.;Vanderkam, E. S.;Gawalt, J. S.;Bocarsly, A. B. Langmuir. 1999, 15, 6598-6600
10. http://www.che.chalmers.se/inst/pol/
11. Wood, A. S. “Tapping the power of intrinsic conductivity”, Modern Plastics Int., Aug. 1991, 33.
12. Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R. N.; Mackay, K.; Friend, R. H.; Burn, P. L.; Holmes, A. B. “Light-emitting diodes based on conjugated polymers” Nature 1990, 347, 539.
13. Gmeiner, J.; Karg, S.; Meier, M.; Rieβ, W.; Strohriegl, P.; Schwoerer, M. “Synthesis, electrical conductivity and electro-luminescence of poly(p-phenylene vinylene) prepared by the precusor route” Acta. Polym. 1993, 44, 201.
14. Gustafsson, G.; Cao, Y.; Treacy, G. M.; Klavetter, F.; Colaneri, N.; Heeger, A. J. “Flexible light-emitting diodes made from soluble conducting polymer” Nature 1992, 357, 477.
15. Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend R. H.; Holms, A. B. “Efficient light-emitting diodes based on polymers with high electron affinities” Nature 1993, 365, 628.
16. http://www.research.Philips.com
17. http://www.uniax.com
18. Braun, D. and Heeger, A. J. Appl. Phys. Lett. 1991, 58, 1982.
19. Burn, P. L.; Holmes, A. B.; Kraft, A.; Bradley, D. D. C.; Brown, A. R. and Friend,R. H. J. Chem. Soc. Chem. Commun. 1992, 32, 59.
20. Burn, P. L.; Holmes, A. B.; Kraft, A.; Bradley, D. D. C.; Brown, A. R.; Friend, R.H. and Gymer, R. W. Nature 1992, 356, 47.
21. Halliday, D. A.; Bradley, D. D. C.; Burn, P. L.; Friend, R. H. and Holmes, A. B. ynth. Met. 1991, 41-43, 931.
22. Greedham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H. and Holmes, A.B. Nature 1993, 365, 628.
23. Zhang, C.; Honger, S.; Pakbaz, K.; Wudl, F. and Heeger, A. J. J. Electro. Mater.1993, 22, 413.
24. Junji Kido, Ypshi Okamoto.; Chem. Rev. 2002, 102, 2357-2368.
25. Frank G. Gao† and Allen J. Bard*''‡;Chem. Mater. 2002, 14, 3465- 3470.
26. 陳柏菁,光訊85期,2000年8月P.27
27. 陳春宏,2003,國立台灣大學化學所碩士論文
28. Baldo, M. A.; O’Brien, D. F.; You, Y.; Shoustikov, A.; Sibley, S.;
Thompson, M. E.; Forrest, S. R. Nature, 1998, 395, 151.
29. 李忠偉,2003,國立清華大學化學所碩士論文
30. Mach, R.;Mueller, G. O. Semicond. Sci. Techno. 1991, 6, 305.
31. Pope, M.; Kailmann, H. P.; Magnate, P. J. Chem Phys. 1963, 38, 2042.
32. Helfrich, W.; Schneider, W. G. J. Chem. Phys. 1966, 44, 2902.
33. Roberts, G. G.; McGinnity, M. M.; Barlow, W. A.; Vincett, P. S. Solid State Commun. 1979, 32, 683.
34. Vincett, P. S.; Barlow, W. A.; Hann, R. A.; Roberts, G. G. Thin Solid Films 1982, 94, 171.
35. Shirota, Y.;Kuwabara, Y.;Inada, H. Appl. Phys. Lett. 1994.
36. Patridge, R. H. Polymer 1983, 24, 733.
37. Burroghes, J. H.; Bradley, D. D. C.; Brown, A. R.; Mackay, R. N.;
Friend, R. H.; Burns, P. L.; Homes, A. B. Nature 1990, 347, 539.
38. A. J. Hegger, B. David, U. S. Patent 5408109, 1992.
39. 顏奚成,旋轉塗佈製程研究,行政院國家科學委員會,1995.
40. Dio, S.; Kuwabara, M.; Noguchi, T. Synth. Met. 1993, 55-57, 4174.
41. Khandwe, M.; Bajpai, U. D. N. Macromolecules 1991, 24, 5203.
42. Belfiere, L. A. Polym. Prepr. 1992, 33, 925.
43. Kohei Tamao, Koji Sumitani, Yoshihisa Kiso, Makoto Kumada, Bull.Chem. Soc. Jap. 1976, 49, 1958.
44. Youssoufi, H. K.; Hmyene, M.; Garnier, F.; Delabouglise, D. J. Chem. Soc. Chem. Commun. 1993, 1550.
45. Collin, J. P.; Sauvage, J. P. J. Chem. Soc., Chem. Commun. 1987, 1075.
46. Ba¨uerle, P.; Sc heib, S. Adv. Mater. 1993, 5, 848.
47. Miyazaki, Y.; Yamamoto, T. Chem. Lett. 1994, 41.
48. Sable, E.; Handel, E.; L’Her, M. Electrochim. Acta. 1991, 36, 15.
49. McCullough, R. D.; Williams, S. P. Chem. Mater. 1995, 7, 2001.
50. Marsella, J. M.; Carroll, P. J.; Swager, T. M.; J. Am. Chem. Soc. 1995, 117, 9831.
51. Brockmann, T. W.; Tour, J. M. J. Am. Chem. Soc. 1995, 117, 4437.
52. Marsella, M. J.; Swager, T. M. J. Am. Chem. Soc. 1993, 115, 12214.
53. Marsella, M. J.; Newland, P. J.; Carrol, P. J.; Swager, T. M. J. Am. Chem. Soc. 1995, 117, 9842.
54. Yamamoto, T.; Zhou, Z.-H.; Maruyama, T.; Yoneda, Y.; Kanbara, T. Chem. Lett. 1990, 223.
55. Yamamoto, T.; Lee, B.-L.; Hayashi, H.; Saito, N.; Maruyama, T. Polymer 1997, 38, 4233.
56. Yamamoto, T.; Saitoh, Y.; Anzai, K.; Fukumoto, H.; Yasuda, T.; Fujiwara, Y.; Choi, B.-K.; Kubota, K.; Miyamae, T. Macromole -cules 2003, 36, 6722-6729
57. Marc Baldo, April 10, 2003 – Organic Optoelectronics – Lecture 17
58. Yasuda, T.; Yamaguchi, I.; Yamamoto, T. Adv. Mater. 2003, 15, 293.
59. Yamamoto, T.; Lee, B.-L.; Hayashi, H.; Saito, N.; Maruyama, T. Polymer 1997, 38, 4233.
60. Leonid, M. G.; Martin, R. B.; Michael, C. P. J. Mater. Chem. 1999, 9, 1957.
61. Crawford, K. B.; Goldfinger, M. B.; Swager, T. M. J. Am. Chem. Soc. 1998, 120, 5187.
62. de Silva, A. P.; Gunaratne, H. Q. N.; Gunnlaugsson, T.; Huxley, A. J. M.; McCoy, C. P.; Rademacher, J. T.; Rice, T. E. Chem. Rev. 1997, 97, 1515.
63. Fluorescent Chemosensors for Ion and Molecule Recognition. ACS Symp. Ser. 1993, 538.
64. McQuade, D. T.; Pullen, A. E.; Swager, T. M. Chem. Rev. 2000, 100, 1537.
65. Zhou, Q.; Swager, T. M. J. Am. Chem. Soc. 1995, 117, 12593.
66. Swager, T. M. Acc. Chem. Res. 1998, 31, 201.
67. Wang, B.; Wasielewski, M, R. J. Am. Chem. Soc. 1997, 119, 12.
68. O’Brien, D. F.; Baldo, M. A.; Thompson, M. E.; Forrest, S. R. Appl.
Phys. Lett., 1999, 74, 442.
69. Baldo, M. A.; Lamansky, S.; Burrows, P. E.; Thompson, M. E.;
Forrest, S. R. Appl. Phys. Lett., 1999, 75, 4.
70. Thompson, M. E.; Burrows, P. E.; Forrest, S. R. Cur. Opinion Solid
State Mater. Sci., 1999, 4, 369.
71. Baldo, M. A.; Thompson, M. E.; Forrest, S. R. Nature, 2000, 403,
750.
72. Alpha, B.; Lehn, J. M.; Mathis, G. Angew. Chem. Int. Ed. Engl. 1987,
26, 266.
73. Hung, L. S.; Cheng, C. H. Materials Science and Engineering R:
Reports 2002, 39, 143.
74. Holmes, R. J.; Forrest, S. R.; Tung, Y. J.; Weong, R. C.; Brown, J. J.;
Garon, S.; Thompson, M. E. Appl. Phys. Lett., 2003, 82, 2422.
75. Holmes, R. J.; D’Andrade, B. W.; Forrest, S. R.; Ren, X.; Li, J.;
Thompson, M. E. Appl. Phys. Lett., 2003, 83, 3818.
76. Adachi, C.; Baldo, M. A.; Thompson, M. E.; Forrest, S. R. J. Appl.
Phys. 2000, 90, 5048.
77. Laurence, A.; Belfiore; Mary Pat McCurdie; EiJi Ueda, Macromolecules 1993, 26, 6908.
78. 林永洲,2003,國立中央大學化學所碩士論文
79. Yamamoto, T.; Osakada, K.; Wakabayashi, T.; Yamamoto, A. Makromol. Chem., Rapid Commun. 1985, 6, 71
80. Yamamoto, T.; Osakada, K.; Kato, K. Makromol. Chem., Rapid Commun. 1989, 190, 1649.
81. Wang, J.; Sheares, V. V.; Macromolecules, 1998, 31, 6769.
82. Pei, J.; Yu,W.-L.; Ni, J.; Lai,Y.-H.; Hung,W.; Heeger, A. J. Macromolecules, 2001, 34, 7241.
83. Ng, S. C.; Lu, H. F.; Chan, H. S. O.; Fujii, A.; Laga, T.; Yoshino, K. Macromolecules 2001, 34, 6895-6903.
84. Frank G. Gao† and Allen J. Bard*''‡. Chem. Mater. 2002, 14, 3465 -3470
85. Melhuish, W. H. J. Phys. Chem. 1961, 65, 229.
86. 徐瑞鴻, 范文祥, “時間解析螢光光譜學”, 科儀新知, 第17卷,
6期, 1996, P.42.
87. Sariciftci, N. S.; Heeger, A. J., Inter. J. Mod. Phys. B., 8, 1994, 237.
88. Samuel, I. D. W.; Crystall, B.; Rumbles, G.; Burn, P. L.; Holmes, A.
B.; Friend, R.H., Chem. Phys. Lett., 213, 1994, 472.
89. Samuel, I. D. W.; Rumbles, G.; Collison, C. J., Phys. Rev. B., 52, 1995,11573.
90. Samuel, I. D. W.; Rumbles, G.; Collison, C. J.; Friend, R. H.; Moratti, S. C.; Holmes, A. B., Synth. Met., 84, 1997, 497.
91. 張恩崇, 1999, 國立清華大學化學工程研究所博士論文.