臺灣博碩士論文加值系統

在本論文中，我們利用鈴木耦合反應合成出一系列新穎的交替共聚合分子，其結構包含有9,9-二辛烷取代的聚芴系高分子為主幹，在其側鏈導入含有嘧啶及吡啶分子取代之1,3,4-氧二唑分子，而在耐熱、光學以及電化學性質中，1,3,4-氧二唑分子對其皆具有可觀的影響力。此外，在溶液和固態的紫外可見光光譜中經由比較發現，固態吸收光譜中其吸收波長具有明顯的紅位移，此意味著高分子即使在支鏈的立體效應下仍有凝集的形成。而在Stern-Volmer曲線圖發現，螢光萃息效應與金屬離子負載量呈正相關的趨勢，且根據光誘導電子轉移機制，此兩高分子乃屬turn-off螢光化學感應器；而在測量對各種金屬離子像是鎳，鋅，銅以及汞陽離子的感應行為中，發現高分子對鎳及銅離子呈現高度感應，並綜合了其對金屬離子的感測結果，顯示了此兩高分子在針對金屬離子的感測中，在靈敏性及選擇性方面皆具有成為高潛力感應系統的材料。

The novel alternating copolymers, poly(9,9-dioctylfluorene) with pendant 2-pyridyl- and 2-pyrimidyl-1,3,4-oxadiazole, were synthesized through palladium-catalyzed Suzuki coupling reaction. The thermal, optical and electrochemical properties of these polymers are substantially affected by the heteroaryl substituted oxadiazole groups in the side chain. In addition, it is interesting to note that the significant bathochromic effect was found which results in different absorption spectra in both solution and solid states. The fluorescence quenching ratios were found to be directly related to the loading of metal ions and can be modeled by a Stern-Volmer type relationship. Due to the photoinduced electron transfer mechanism, the polymers act as the turn-off fluorescent chemosensor. The sensing behaviors to various metal ions such as nickel(II) cations, zinc(II) cations, cupper(II) cations and mercury(II) cations revel that the polymers are highly sensitive to nickel(II) cations and cupper(II) cations. The results show that these two polymers can act as the potential sensory material for the appropriate detection of sensitive and selective sense of metal ions.

List of Contents

List of Contents I
Appendix . NMR and Mass spectra IV
List of Figures VI
List of Schemes X
List of Tables XI
Abstract XII
中文摘要 XIII
Acknowledgements XIV
Chapter 1. Introduction and Aims 1
1.1 Introduction 2
1.2 Introduction to Organic Semiconductor 3
1.2.1 Conducting polymers 3
1.2.2 Band theory of Solids 5
1.2.2 Excitations in conjugated polymers 6
1.2.3 Luminescence 9
1.2.4 Electroluminescence in OLEDs 14
1.3 Fluorescenct chemosensor and its application 16
1.3.1 Introduction to sensors 16
1.3.2 The mechanism of analytes detection 18
1.3.3 Fluorescent conjugated polymers as chemosensors 23
1.4 Introduction to polyfluorene 26
1.5 Aims of this project 28
1.6 Reference 29
Chapter 2. Results and Discussion 32
2.1 Introduction to oxadiazoles 33
2.2 Synthesis and characterization of monomers 36
2.2.1 2,7-dibromofluorene 36
2.2.2 2,7-bis(4,4,5,5,-tetramethyl-[1,3,2]dioxaborolan-2-yl)-9,9-dioctyl- fluorene 38
2.2.3 Synthetic routes to 2,5-diaryl-1,3,4-oxadiazoles 41
2.3 Preparation and characterization of polymers 48
2.3.1 Synthesis of poly(2,7-(9,9-dioctyl)fluorene-alt-2,5-4-[(2’-pyridyl)- 1,3,4’-oxadiazol-5’-yl]phenylene) and poly(2,7-(9,9-dioctyl)fluorene- alt-2,5-4-[(2’-pyridyl)-1,3,4’-oxadiazol-5’-yl]phenylene) 48
2.3.2 Molecular weight and structure characterization 49
2.4 Optical properties 55
2.5 Responsive properties on metal ions 59
2.6 Electrochemical and thermal properties of polymers 64
2.7 Summary 67
2.8 Reference 68
Chapter 3. Conclusions 71
3.1 Conclusions 72
Chapter 4. Experimental 73
4.1 General procedure 74
4.2 Synthesis of monomer 75
4.2.1 Synthesis of 2,7-dibromo-9,9-dioctyl-9H-fluorene 75
4.2.2 Synthesis of 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-
dioctylfluorene 75
4.2.3 Synthesis of 3,5-dibromobenzoic hydrazide 76
4.2.4 Synthesis of 2-(5-(3,5-dibromophenyl)-1,3,4-oxadiazol-2-yl) pyridine 77
4.2.5 Synthesis of 2-(5-(3,5-dibromophenyl)-1,3,4-oxadiazol-2-yl) pyrimidine 78
4.3 Synthesis of alternating copolymers 78
4.3.1 Synthesis of poly(2,7-(9,9-dioctyl)fluorene-alt-2,5-4-[(2’-pyridyl)- 1,3,4’-oxadiazol-5’-yl]phenylene) 78
4.3.2 Synthesis of poly(2,7-(9,9-dioctyl)fluorene-alt-2,5-4-[(2’-pyrimidyl)- 1,3,4’-oxadiazol-5’-yl]phenylene) 79
Appendix. NMR and Mass Spectra 81

Chapter 1

[1] A. Kraft, A. C. Grimsdale, A. B. Holmes, Angew. Chem. Int. Ed. 1998, 37, 402.
[2] C. K. Chiang, C. B. Fincher, Jr., Y. W. Park, A. J. Heeger, H. Shirakawa, E. J. Louis, S. C. Gau, A. G. MacDiarmid, Phys. Rev. Lett., 1977, 39, 1098.
[3] C. W. Tang, S. A. VanSlyke, Appl. Phys. Lett., 1987, 51, 913.
[4] H. N. Kim, Z. Guo, W. Zhu, J. Yoon, H. Tian, Chem. Soc. Rev., 2011, 40, 79.
[5] A. F. Li, Y. B. Ruan, Q. Q. Jiang, W. B. He, Y. B. Jiang, Chem. Eur. J., 2010, 16, 5794.
[6] A. O. Patil, A. J. Heeger, F. Wudl, Chem. Rev, 1988, 88, 183.
[7] C. J. Shi, Y. Yao, Y. Yang, Q. B. Pei, J. Am. Chem. Soc., 2006, 128, 8980.
[8] H. Suh, Y. Jin, S. H. Park., D. Kim., J. Kim, C. Kim, J. Y. Kim, K. Lee, Macromolecules., 2005, 38, 6285.
[9] A. Zen, M. Saphiannikova, D. Neher, U. Asawapirom, U. Scherf, Chem. Mater., 2005, 17, 781.
[10] G. Hadziioannou, P. F. V. Hutten, Semiconducting Polymer - Chemistry, Physics and Engineering, 1999, Wiley-VCH: Weinheim.
[11] G. Horowitz, Adv. Mater., 1998, 10, 365.
[12] C. L. Pai, C. L. Liu, W. C. Chen, S. A. Jenekhe, Polymer, 2006, 47, 699.
[13] A. J. Heeger, Revies of Morden Physics, 2007, 73, 681.
[14] H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang, A. J. Heeger, Chem. Commun., 1977, 578.
[15] T. Schimmel, M. Schwoerer, H. Naarmann, Synth. Met., 1990, 37, 1.
[16] H. Shirakawa, Angew. Chem. Int. Ed., 2001, 40, 2574.
[17] H. Nishikiori, N. Tanaka, K. Takagi ,T. Fujii, Res. Chem. Intermed., 2003, 29, 485.
[18] M. Pope, H. Kallmann, P. Magnante, Electroluminescence in organic crystals. J. Chem. Phys. 1963, 38, 2042.
[19] L. C. Clark, C. L.yons, N. Y. Ann, Acad Sci, 1962, 102, 29.
[20] L. J. Fan, Y. Zhang, C. B. Murphy, S. E. Angell, Coord. Chem. Rev., 2009, 253, 413.
[21] B. Valeur, I. Leray, Coord. Chem. Rev., 2000, 205, 3.
[22] J. Bourson, B. Valeur, J. Phys. Chem., 1989, 93, 3871.
[23] M. J. Marsella, R. J. Newland, P. J. Carroll, T. M. Swager, J. Am. Chem. Soc., 1995,117, 9842.
[24] H. B. Laurent, A. Castellan, M. Daney et al., J. Am. Chem. Soc., 1986, 108, 315.
[25] I. Aoki, H. Kawabata, K. Nakashima, S. Shinkai, J. Chem. Soc. Chem. Commun., 1991, 1771.
[26] M. E. A. Fegley et al., Inorg. Chim. Acta, 2012, 381, 78.
[27] L. J. Fan et al., Coord. Chem. Rev., 2009, 253, 410.
[28] T. M. Swager., Acc. Chem. Res., 1998, 31, 201.
[29] B. Wang, M. R. Wasielewski, J. Am. Chem. Soc., 1997, 119, 12
[30] D. McQuade, A. Pullen, T. Swager, Chem. Rev., 2000, 100, 2537.
[31] F. G. Bordwell, G. J. McCollum, J. Org. Chem., 1976, 41, 2391.
[32] M. Fukuda, K. Sawaka, K. Yoshino, Jpn. J. Appl. Phys., 1989, 28, 1433.
[33] C. E. Brown, P. Kovacic, C. A. Wilkie , J. A. Kinsinger, R. E. Hein, S. I. Yaniger, R. B. Cody, Jr. ibid., 1989, 24, 255.
[34] T. Yamamoto, Prog. Polym. Sci., 1992, 17, 1153.
[35] Ranger M., M. Leclerc, J. Chem. Soc. Chem. Commun., 1997, 1597.

Chapter 2

[1] A. B. Descalzo, K. Rurack, H. Weisshoff, M. M. Ramon, M. D. Marcos,
P. Amoros et al., J. Am. Chem. Soc., 2005, 127, 184.
[2] R. Badugu, J. R. Lakowicz, C. D. Geddes, J. Am. Chem. Soc., 2005, 127, 3635.
[3] Y. L. Tang, F. D. Feng, F. He, S. Wang, D. B. Zhu, J. Am. Chem. Soc., 2006, 128, 14972.
[4] G. Lu, J. E. Grossman, J. B. Lambert, J. Org. Chem., 2006, 71, 1769
[5] U. Mitschke, P. Bӓuerle, J. Mater. Chem., 2000, 10, 1471.
[6] S. H. Mashraqui, R. S. Kenny, G. G. Shailesh, A. Krishnan, M. Bhattacharya,
P. K. Das, Opt. Mater., 2004, 27, 257.
[7] N. C. Yang, J. K. Jeong, D. H. Suh, Chem. Lett., 2003, 32, 40.
[8] Y. Chen, C. K. Liao, T. Y. Wu, Polymer, 2002, 43, 4545.
[9] S. Janietz, S. Anlauf, A. Wedel, Synth. Met., 2001, 112, 11.
[10] Z. Peng, J. Zhang, Chem. Mater., 1999, 11, 1138.
[11] B. Xu, Y. Pan, J. Zhang, Z. Peng, Synth. Met., 2000, 114, 337.
[12] H. H. Sung, H. C. Lin, Macromolecules, 2004, 37, 7945.
[13] J. F.Wang, G. E. Jabbour, E. A. Mash, J. Anderson, Y. Zhang, P. A. Lee, N. R. Armstring, Adv. Mater., 1999, 11, 1266.
[14] O. Bolton, J. Kim, J. Mater. Chem., 2007, 17, 1981.
[15] G. Zhou, Y. Cheng, L. Wnag, X. Jing, F. Wang, Macromolecules, 2005, 38, 2148.
[16] T. H. Kim, H. J. Kim, C. G. Kwak, W. H. Park, T. S. Lee, J. Polym. Sci., Part A: Polym. Chem., 2006, 44, 2059.
[17] Y. Liu, L. Zong, L. Zheng, L. Wu, Y. Cheng, Polymer, 2007, 6799.
[18] A. F. Li, Y. B. Ruan, Q. Q. Jiang, W. B. He, Y. B Jiang, Chem. Eur. J., 2010, 16, 5794.
[19] B. S. Orlek et al., J. Med. Chem., 1991, 34, 2726.
[20] W. R. Tully et al., R. J. Med. Chem., 1991, 34, 2060.
[21] F. A. Omar, N. M. Mahfouz, M. A. Rahman, Eur. J. Med. Chem., 1996, 31, 819.
[22] C. Dobrota, C. C. Paraschivescu, I. Dumitru, M. Matache, I. Baciu, L. L. Rut, Tetrahedron Lett., 2009, 50, 1886.
[23] C. O. Kangani, B. W. Day, Tetrahedron Lett., 2009, 50, 5332.
[24] V. Padmavathi, G. S. Reddy, A. Padmaja, P. Kondaiah, A. Shazia, Eur. J. Med. Chem., 2009, 44, 2106.
[25] S. Borg, R. C. Vollinga, M. Labarre, K. Payza, L. Terenius, K. Luthman, J. Med. Chem., 1999, 42, 4331.
[26] S. H. Lee, H. J. Seo, M. J. Kim, S. Y. Kang, K. S. Song, S. H. Lee, M. E. Jung, J. Kim, J. Lee, Bioorg. Med. Chem. Lett., 2009, 19, 1899.
[27] Y. Wang, D. R. Sauer, S. W. Djuric, Tetrahedron Lett., 2006, 47, 105.
[28] P. Stabile, A. Lamonica, A. Ribecai, D. Castoldi, G. Guercio, O. Curcuruto, Tetrahedron Lett., 2010, 51, 4801.
[29] K. Okamoto, K. L. Christine, Polym. Chem., 2011, 2, 2424.
[30] B. Xu, Y. Pan, J. Zhang, Z. Peng, Synth. Met., 2000, 114, 337.
[31] D. F. Eaton, Pure Appl. Chem., 1988, 60 ,1107.
[32] S. H. Mashraqui, S. Sundaram, A. C. Bhasikuttan, Tetrahedron, 2007, 63,1680
[33] M. E. A. Fegley et al., Inorganica Chimica Acta, 2012, 381, 78.
[34] S. W. Thomas, G. D. Joly, T. M. Swager, Chem Rev, 2007, 107, 1339.
[35] A. M. Spring, C . Y. Yu, M. Horie, M. L. Turner, Chem. Commun., 2009, 2676.