臺灣博碩士論文加值系統

本篇論文合成了以吡咯並[3,2-b]吡咯為中心的一系列化合物，在其二、五號位上分別接上三苯胺、咔唑及噻吩等基團，探討其電化學、光物理與光化學性質。其中化合物4具有電聚的潛力，已初步探討了其電聚合與電致變色的行為。而化合物1在具有鹵化物的環境下有光化學反應變色的情形，以UV-Vis-NIR光譜追蹤分析推測出其可能的反應機制，並進一步用作鹵化物偵測，以肉眼辨識變色水中的三氯甲烷濃度最低可達8 ppm。此外，此一系列化合物皆有很強的螢光強度，在光電材料的應用上是具有潛力的新型染料。

A series of compounds with pyrrolo [3,2-b] pyrrole-centered have been synthesized, containing triphenylamine, carbazole, and thiophene group at the 2, 5-position. The electrochemical, photophysics and photochemistry properties were investigated. Compound 4 have show potential for electrochemical polymerization, and its electrochromic mechanism has been studied. Compound 1 in the environment with halides proceeds a photochemical reaction and is observed change color. The possible reaction mechanism have been studied by UV-Vis-NIR spectrum analysis, and further used to detect halide, which can visually identify chloroform in water to lowest concentration of 8 ppm. Additionally, this series of compounds have strong fluorescence intensity, having potential to be novel dyes in the application of photovoltaic materials.

中文摘要 IV
Abstract V
圖目錄 VI
表目錄 XII
流程目錄 XIII
化合物結構與編號 XV
第一章 緒論 1
1.1 前言 1
1.2 1,4-氫吡咯並[3,2-b]吡咯 3
1.3 氧化電聚合 9
1.4 研究動機與分子設計 12
第二章 結果與討論 15
2.1 合成策略及方法 15
2.2 X-ray 晶體結構分析 22
2.3 電化學性質分析 29
2.4 光譜電化學分析 45
2.5 光物理性質分析 50
2.6 光化學分析 53
2.7 光反應速度比較 67
2.8 鹵化物偵測實驗 72
第三章 結論 79
第四章 實驗部分 80
4.1 實驗儀器與試劑 80
4.1.1 實驗儀器 80
4.1.2 實驗試劑 81
4.2 合成步驟 82
第五章 參考文獻 91
附錄一 化合物之X-ray晶體參數表、鍵長與鍵角資料 94
化合物1之晶體結構 94
化合物2之晶體結構 102
化合物3之晶體結構 107
附錄二 化合物之氫核磁共振光譜及碳核磁共振光譜 112
化合物1之1H光譜 112
化合物3之1H光譜 113
化合物3之13C光譜 114
化合物4之1H光譜 115
化合物4之13C光譜 116
化合物6之1H光譜 117
化合物6之13C光譜 118
化合物7之1H光譜 119
化合物7之13C光譜 120
化合物8之1H光譜 121
化合物8之13C光譜 122

[1] (a) E Lim, B. J. Jung, H. K. Shim, Macromolecules 2003, 36, 4288–4293; (b) I. Mcculloch, M. Heeney, C. Bailey, K. Genevicius, I. Macdonald, M. Shkunov, D. Sparrowe, S. Tierney, R. Wagner, W. M. Zhang, M. L. Chabinyc, R. J. Kline, M. D. Mcgehee, M. F Toney, Nat. Mater. 2006, 5, 328-333; (c) H. Bronstein, Z. Y. Chen, R. S. Ashraf, W. M. Zhang, J. P. Du, J. R. Durrant, P. S. Tuladhar, K. Song, S. E. Watkins, Y. Geerts, M. M. Wienk, R. A. J. Janssen, T. Anthopoulos, H. Sirringhaus, M. Heeney, I. McCulloch, J. Am. Chem. Soc. 2011, 133, 3272–3275.
[2] (a) S. Soth, M. Farnier, Can. J. Chem. 1978, 56, 1429–1434; (b) S. Gronowitz, C. Westerlund, A. B. Hçrnfeldt, Acta Chem. Scand. 1976, 30b, 391–396; (c) H. R. Snyder, L. A. Carpino, J. F. Zack, J. F. Mills, J. Am. Chem. Soc. 1957, 79, 2556–2559; (d) D. S. Matteson, H. R. Snyder, J. Org. Chem. 1957, 22, 1500–1504; (e) S. Srinivasan, G. B. Schuster, Org. Lett. 2008, 10, 3657 –3660; (f) I. Alkorta, F. Blanco, J. Elguero, THEOCHEM 2008, 851, 75–83.
[3] A. Janiga, D. T. Gryko, Chem. Asian J. 2014, 9, 3036 – 3045.
[4] A. Janiga, E. Głodkowska-Mrówka, T. Stokłosa, D. T. Gryko, Asian J. Org. Chem. 2013, 2, 411–415.
[5] H. Hemetsberger, D. Knittel, Monatsh. Chem.. 1972, 103, 194 –204.
[6] (a) M. L. R. Heffernan, J. M. Dorsey, M. James, Q. K. Fang, R. J. Foglesong, S. C. Hopkins, M. L. Jones, S. W. Jones, C. O. Ogbu, J. B. Perales, M. Soukri, U.S. Pat. Appl. Publ., US 20080058395A1, 2008; (b) A. J. Barker, J. G. Kettle, A. W. Faull, PCT Int. Appl., WO 9940914A1, 1999; (c) B. P. Murphy, R. W. Glenn, M. Lim, J. M. Gardlik, S. D. Jones, W. D. Laidig, J. D. Shaffer. PCT Int. Appl., WO 2005077324A1, 2005.
[7] T. Aratani, H. Yoshihara, G. Suzukamo, Tetrahedron Lett. 1989, 30, 1655 – 1656.
[8] B. J. Stokes, H. Dong, B. E. Leslie, A. L. Pumphrey, T. G. Driver, J. Am. Chem. Soc. 2007, 129, 7500 – 7501.
[9] (a) H. Prinzbach, R. Schwesinger, M. Breuninger, B. Gallenkamp, D. Hunkler, Angew. Chem. Int. Ed. Engl. 1975, 14, 348 –350; Angew.Chem. 1975, 87, 350–351; (b) H. Prinzbach, Chimia 1979, 33, 332–334.
[10] T. Kumagai, K. Satake, K. Kidoura, T. Mukai, Tetrahedron Lett. 1983, 24, 2275–2278.
[11] T. Kumagai, S. Tanaka, T. Mukai, Tetrahedron Lett. 1984, 25, 5669–5672.
[12] (a) T. Mukai, T. Kumagai, S. Tanaka, (Jpn. Kokai Tokkyo Koho), JP 62212389A, 1987; (b) T. Akitani, H. Yoshihara, S. Taguchi, (Jpn. Kokai Tokkyo Koho), JP 01172388A, 1989.
[13] H. T. Dieck, U. Verfürth, K. Diblitz, J. Ehlers, G. Fendesak, Chem. Ber. 1989, 122, 129–131.
[14] (a) D. T. Gryko, A. Janiga, M. Krzeszewski, PCT/PL2013/050025, 2013; (b) M. Krzeszewski, B. Thorsted, J. Brewer, D. T. Gryko, J. Org. Chem. 2014, 79, 3119 –3128.
[15] (a) H. Debus, Justus Liebigs Ann. Chem. 1858, 107, 199; (b) B. Radziszewski, Ber. Dtsch. Chem. Ges. 1882, 15, 1493.
[16] D. S. Rampon, L. A. Wessjohann, Paulo H. Schneider, J. Org. Chem. 2014, 79, 5987−5992.
[17] M. Rusalov, S. Druzhinin, B. Uzhinov, Journal of Fluorescence 2004, 14, 193-202.
[18] A. T. R. Williams, S. A. Winfield, J. N. Miller, Analyst 1983, 108, 1067-1071
[19] H. Z. Liu, R. C. Bo, H. F. Liu, N. J. Li, Q. F. Xu, H. Li, J. M. Lu, L. H. Wang, J. Mater. Chem. C, 2014, 2, 5709–5716.
[20] C. Y. Kuo, Y. C. Huang, C. Y. Hsiow, Y. W. Yang, C. I. Huang, S. P. Rwei, H. L. Wang, L. Y. Wang, Macromolecules 2013, 46, 5985−5997.