本研究藉由控制P(4-FlSty)和PNNEPS的立體規則性來探討高分子立體規則性對光致放光行為的影響。此外，調控不同的高分子規則度和化學官能基的修飾也將會被探討其現象。在P(4-FlSty)系統中，PL圖譜有多個放光峰，藉由生命週期螢光儀來證明其具不同立體規則性之高分子包含單體放光和聚集放光。在稀薄溶液狀態，由於出色的溶解度使不同立體規則度具有近乎相同的放光行為。在THF和H2O的混合溶液中，隨著水的量逐漸增加放光強度有先減弱在增強的趨勢，其原因在π-π interaction和restriction of intramolecular rotation (RIR)競爭下的結果。此外比起P(4-FlSty)15 (rr=98%, mm=0%)和P(4-FlSty)12 (rr=62%, mm=19%)，P(4-FlSty)14 (rr=29%, mm=61%)展現特別明顯的excimer放光。在固體薄膜狀態，不同立體規則度高分子在光致發光行為上的差異將更加明顯。在UV光照射下，薄膜的放光由紫色轉變為青藍色。在PNNDPS系統中，隨著水的量增加，低規則度高分子如PNNDPS9.8 (rr=53%, mm=24%)和PNNDPS11.9 (rr=62%, mm=22%)由於RIR效應使得放光強度逐漸增加。相反的，高規則度的高分子如PNNDPS12 (rr=83%, mm=7%)放光強度隨著水的量增加而減弱，原因由ultraviolet-visible吸收圖譜證明其在聚集的過程中有嚴重的H-aggregation產生。此外PNNDPS12 (rr=83%, mm=7%)具有高立體規則度，我們在THF/water = 3/7狀態下由穿透式電子顯微鏡找到有結晶現象，並且對應有些微的放光增強，確立了此高分子具有aggregation-caused quenching (ACQ)和crystallization-induce emission enhancement (CIEE)兩種性質。由以上兩個系統一系列的分析，證實對於高分子的光致發光行為而言立體規則度確實扮演重要的角色，這在設計光致放光高分子於現實生活應用上是一個全新的概念。

A series of stereoregular polymers including atactic, syndiotactic and isotactic poly(9,9-Dibutyl-2-(4-vinylphenyl)-9H-fluorene) [P(4-FlSty)] and poly 4(N,N-diphenyl)styrene [PNNDPS] were synthesized to exam tacticity effect on photoluminescence (PL). In P(4-FlSty) systems, the PL spectra reveal multiple PL emissive bands including monomeric and excimer emissions evidenced by life-time spectroscopy. In dilute solution of THF, the similar emissive behavior for the stereoregular polymers is found to the excellent chain mobility of polymer chains. In THF/water mixtures, the PL intensity of the P(4-FlSty) initially decreases and then dramatically increase with the increases of the water contents. This variation might result from the competition between the π-π interaction and the restriction of intramolecular rotation (RIR) effect. Also, the P(4-FlSty)14 (rr=29%, mm=61%) exhibit the dramatic increase of excimer emission in comparison with the P(4-FlSty)15 (rr=98%, mm=0%) and P(4-FlSty)12 (rr=62%, mm=19%). Furthermore, this difference is further enlarged as the stereoregular polymers in film state, revealing the emissive colors from indigo to cyan with the increase of the isotacticity under UV illumination. For the PNNDPS system, the PL spectra of the stereoregular polymers reveal three PL emissive bands involving monomeric and excimer emissions in dilute solution. In aggregation solutions, the PL spectra display enhanced PL emission for PNNDPS9.8 (rr=53%, mm=24%) and PNNDPS11.9 (rr=62%, mm=22%) as the water content increases in the THF/water mixtures, due to the RIR effect. Notably, with the increase of the water contents, the PL emission decreases significantly in the PNNDPS12 (rr=83%, mm=7%) due to the formation of H-aggregation evidenced by ultraviolet-visible (UV-Vis) spectra. Owing to the very high syndiotacticity in the PNNDPS12 (rr=83%, mm=7%), we found that the crystallization may induce the enhancement of PL emission as THF/water = 3/7, evidenced by selected area electron diffraction (SAED) of transmission electron microscopy (TEM). Consequently, the syndiotacticity of the chain configuration results in aggregation-caused quenching (ACQ), whereas the crystallization may give rise to crystallization-induce emission enhancement (CIEE) in the PNNDPS system. We thus suggest that the PNNDPS12 (rr=83%, mm=7%) possesses dual ACQ-active and CIEE-active properties. Therefore, the tacticity for stereoregular polymers with pendant flourophores indeed plays an important role on the PL behavior, which may provide a novel concept in the design of photoluminescent polymers for applications.

論文審定書　i
致謝　ii
中文摘要　iii
Abstract　 iv
Contents　vi
List of Figures　viii
List of Tables　xvii
Chapter 1 Introduction　1
　1.1 Principle of Photoluminescence　1
　1.2 Excimer and Aggregation Emissions　4
　1.3 H-aggregation and J-aggregation　8
　1.4 Self-assembly on Photoluminescence　9
　　1.4.1 Aggregation-Caused Quenching (ACQ)　9
　　1.4.2 Twist Intramolecular Charge Transfer (TICT)　10
　　1.4.3 Aggregation-Induced Emission (AIE)　12
　　1.4.4 Crystallization-Induce Emission (CIE)　15
　　1.4.5 Aggregation-Enhanced Excimer Emission (AEEE)　17
　　1.4.6 Fluorescence Decay Dynamics　18
　1.5 Photoluminescence of Polymeric Materials　20
　　1.5.1 Main-Chain conjugated polymers　20
　　1.5.2 Side-Chain conjugated polymers　24
　1.6 Stereoregular Polymers　30
　Chapter 2 Objectives　34
　Chapter 3 Experimental Section 36
　Chapter 4 Results & Discussion 42
　4.1 Photoluminescent P(4-FlSty) system　41
　　4.1.1 Thermal Stability　41
　　4.1.2 Thermal Behavior　43
　　4.1.3 Photoluminescence of the Stereoregular P(4-FlSty) Polymers in Dilute Solution　45
　　4.1.4 Photoluminescence of the Stereoregular P(4-FlSty) Polymers in Aggregation Solution　51
　　4.1.5 PL Behavior of Stereoregular P(4-FlSty) Polymers in Thin Film　66
　　4.1.6 Tacticity Effect on PL Behavior of Stereoregular P(4-FlSty) Polymers with Pendant Fluorophores　69
　4.2 Photoluminescent PNNDPS system　74
　　4.2.1 Thermal Stability　74
　　4.2.2 Thermal Behavior　76
　　4.2.3 Photoluminescence of the Stereoregular PNNDPS Polymers in Dilute Solution　　79
　　4.2.4 Photoluminescence of the Stereoregular PNNDPS Polymers in Aggregation Solution　81
　　4.2.5 PL Behavior of Stereoregular PNNDPS Polymers in Thin Film　93
　　4.2.6 Tacticity Effect on PL Behavior of Stereoregular PNNDPS Polymers with Pendant Fluorophores　95
　Chapter 5 Conclusions 99
　Chapter 6 References 101

Chapter 6: References
1. M. Grätzel and J. K. Thomas, in Modern Fluorescence Spectroscopy, edited by E. L. Wehry (Plenum, New York, 1976), Vol. 2, p. 169.
2. Birks, J. B. Excimers Rep. PRog. Phys. 1975, 38, 903.
3. Birks, J. B.; Christophorou, L. G. Spectrochim. Acta. 1963, 19, 401.
4. Birks, J. B.; Lumb, M. D.; Munro, I. H. Proc. R. Soc. London 1963, 275, 575.
5. Wilhelm, M.; Zhao, C.-L.; Wang, Y.; Xu, R.; Winnik, M. A. Macromolecules 1981, 24, 1033.
6. Jhaveri, S. B.; Beinhoff M.; Hawker, C. J.; Carter, K. R.; Sogah, D. Y. ACS nano 2008, 2, 719.
7. Sagara, Y.; Kato, T. Angew. Chem. Int. Ed. 2008, 47, 575.
8. Birks, J. B. Photophysics of Aromatic Molecules Wiley, London, 1970
9. Robertson, J. M.; White, J. G. J. Chem. Soi. 1947, 358.
10. Camerman, A.; Trotter, J. Acta. Cryst. 1965, 18, 636.
11. Herz, A. H. Adv. Colloid Interface Sci. 1977, 8, 237.
12. Mӧbius, D. Adv. Mater. 1995, 7, 437.
13. Egorov, V. V. J. Chem. Phys. 2002, 116, 3090.
14. Knoester, J. Int. J. Photoenergy 2006, 5, 4.
15. Förster, Th.; Kasper, K. Z. Phys. Chem. (Munich) 1954, 1, 275.
16. Malkin, J. Photophysical and Photochemical Properties of Aromatic Compounds CRC, Boca Raton, 1992.
17. Turro, N. J. Modern Molecular Photochemistry University Science Books, Valley, M. 1991.
18. Li, X. C.; Moratti, S. C. in Photonic Polymer Systems Dekker, M. New York, 1998.
19. Hong, Y.; Lam, W. Y.; Tang, B. Z. Chem. Comm. 2009, 4332.
20. Liu, J.; Lam, W. Y.; Tang, B. Z. J. Inorg. Organomet. Polym. 2009, 19, 249.
21. Thomas III, S. W.; Joly, G. D.; Swager, T. M. Chem. Rev. 2007, 107, 1339.
22. Belletête, M.; Bouchard, J.; Leclerc, M.; Durocher, G. Macromolecules 2005, 38, 880.
23. Menon, A.; Galvin, M.; Walz, K. A.; Rothberg, L. Synth. Met. 2004, 141, 197.
24. Chen, C.-T. Chem. Mater. 2004, 16, 4389.
25. Grell, M.; Bradley, D. D. C.; Ungar, G.; Hill, J.; Whitehead, K. S. Macromolecules 1999, 32, 5810.
26. Jakubiak, R.; Collison, C. J.; Wan, W. C.; Rothberg, L. J. Phys. Chem. A 1999, 103, 2394.
27. Grell, M.; Bradley, D. D. C.; Long, X.; Chamberlain, T.; Inbasekaran, M.; Woo, E. P.; Soliman, M. Acta Polym. 1998, 49, 439.
28. Lemmer, U.; Heun, S.; Mahrt, R. F.; Scherf, U.; Hopmeier, M.; Siegner, U.; Gobel, E. O.; Müllen, K.; Bassler, H. Chem. Phys. Lett. 1995, 240, 373.
29. Slavík, J. Fluorescence Microscopy and Fluorescent Probes, Plenum, New York, 1996.
30. Valeur, B. Molecular Fluorescence: Principle and Applications Wiley-VCH, Weinheim, 2002
31. Advanced Concepts in Fluorescence Sensing, ed. Geddes, C. D.; Lakopwicz, J. R.; Springer; Norwell 2005.
32. Fluorescence Sensors and Biosensors, ed. Thompson; R. B. CRC, Boca Raton, 2006.
33. Tan, W. H.; Wang, K. M.; Drake, T. J. Curr. Opin. Chem. Biol. 2004, 8, 547.
34. Sapsford, K. E.; Berti, L.; Medintz, I. L. Angew. Chem. Int. Ed. 2006, 45, 4562.
35. Borisov, S. M.; Wolfbeis, O. S. Chem. Rev. 2008, 108, 423.
36. Grimsdale, A. C.; Müllen, K. Adv. Polym. Sci. 2008, 212, 1.
37. Wong, W.W. H.; Holmes, A. B. Adv. Polym. Sci. 2008, 212, 85.
38. Boudreault, P. L. T.; Blouin, N.; Leclerc, M. Adv. Polym. Sci. 2008, 212, 99.
39. Sanchez; J. C.; Trogler, W. C. Macromol. Chem. Phys. 2008, 209, 1527.
40. Zhang, Y.; Liu, B.; Cao, Y. Chem.–Asian J. 2008, 3, 739.
41. Luo, J.; Xie, Z.; Lam, J. W. Y.; Cheng, L.; Chen, H.; Qiu, C.; Kwok, H. S.; Zhan, X.; Liu, Y.; Zhu, D.; Tang, B. Z. Chem. Commun. 2001, 1740.
42. Tang, B. Z.; Zhan, X.; Yu, G.; Lee, P. P. S.; Liu, Y.; Zhu, D. J. Mater. Chem. 2001, 11, 2974.
43. Gustafsson, G.; Gao, Y.; Treacy, G. M.; Klavetter, F.; Colaneri, C.; Heeger, A. J. Nature 1992, 357, 477.
44. Wang, P. W.; Liu, Y. J.; Devadoss, C.; Bharathi, P.; Moore, J. S. Adv. Mater. 1996, 8, 237.
45. Freeman, A. W.; Koene, S. C.; Malenfant, P. R. L.; Thompson, M. E.; Frechet, J. M. J. J. Am. Chem. Soc. 2000, 122, 12, 385.
46. Baskar, C.; Lai, H. Y.; Valiyaveettil, S. Macromolecules 2001, 34, 6255.
47. Halls, J. J. M.; Walls, C. A.; Greenham, N. C.; Marseglia, E. A.; Friend, R. H.; Moratti, S. C.; Holmes, A. B. Nature 1995, 376, 498.
48. Szczesna, M.; Galas, E.; Bielecki, S. J. Mol. Catal. B 2000, 111, 671.
49. Heeger, P. S.; Heeger, A. J. Proc. Natl. Acad. Sci. USA 1999, 96, 12, 219.
50. Schenning, A.; Peeters, E.; Meijer, E. W. J. Am. Chem. Soc. 2000, 122, 4489.
51. Hecht, S.; Frechet, J. M. J. Angew. Chem. Int. Ed. 2001, 40, 74.
52. Scherf, U. J. Mater. Chem. 1999, 9, 1853.
53. Hide, F.; Diaz-Garcia, M. A.; Schwartz, B. J.; Heeger, A. J. Acc. Chem. Res. 1997, 30, 430.
54. Z. J. Zhao, S. M. Chen, J. W. Y. Lam, Z. M Wang, P. Lu, F. Mahtab, H. H. Y. Sung, I. D. Williams, Y .G. Ma, H. S. Kwok and B. Z. Tang, Pyrene-Substituted Ethenes: Aggregation-Enhanced Excimer Emission, J. Mater. Chem. 2011, 21, 7210–7216.
55. Y. Ren, J.W.Y. Lam, Y. Q. Dong, B. Z. Tang and K. S. Wong, Enhanced Emission Efficiency and Excited State Lifetime Due to Restricted Intramolecular Motion in Silole Aggregates, J. Phys. Chem. B 2005, 109, 1135–1140.
56. Friend, R. H.; Gymer, R. W.; Holmes, A. B.; Burroughes, J. H.; Marks, R. N.; Taliani, C.; Bradley, D. D. C.; Dos Santos, D. A.; Brédas, J.-L.; Lӧgdlund, M.; Salaneck, W. R. Nature 1999, 397, 121.
57. Braun, D.; Heeger, A. J. Appl. Phys. Lett. 1991, 58, 1982.
58. Gustafsson, G.; Cao, Y.; Treacy, G. M.; Klavetter, F.; Colinari, N.; Heeger, A. J. Nature 1992, 357, 477.
59. Bharathan, J.; Yang, Y. Appl. Phys. Lett. 1998, 72, 2660.
60. Hebner, T. R.; Wu, C. C.; Marcy, D.; Lu, M. H.; Strum, J. C. Appl.Phys. Lett. 1998, 72, 519.
61. Blouin, N.; Michaud, A.; Leclerc, M. Adv. Mater. 2007, 19, 2295.
62. Innis, P. C.; Masdarolomoor F.; Kane-Maguire, L. A. P.; Forster, R. J.; Keyes, T. E.; Wallace, G. G. J. Phys. Chem. B 2007, 111, 12738.
63. Li, Y.; Vamvounis, G.; Holdcroft, S. Macromolecules 2002, 35, 6900.
64. Bunz, U. H. F.; Imhof, J. M.; Bly, R. K.; Bangcuyo, C. G.; Rozanski, L.; Vanden Bout, D. A. Macromolecules 2005, 38, 5892.
65. Samuel, I. D. W.; Rumble, G.; Friend, R. H.; In Primary Photoexcitations in Conjugated Polymers: Molecular Excitation versus Semiconductor Band Model; Sariciftci, N. S., Ed.; World Scientific Publishing Co.: Singapore, 1997.
66. Science 2002, 295, 2313-2556. Special issue on Supramolecular Chemistry and Self-Assembly. In particular: Lehn, J. M. Science 2002, 295, 2400-2402.
67. Yarari, S. S.; Bovey, F. A.; Lumry, R. Nature 1963, 200, 242.
68. Vala, M. T.; Haebig, J.; Rice, S. A. J. Chem. Phys. 1965, 43, 886.
69. Longworth, J. W. Biopolymers 1966, 4, 1131.
70. Gebler, D. D.; Wang, Y.Z.; Fu, D, -K.; Swager, T. M.; Epstein, A. J. J. Chem. Phys.1998.
71. Johnson, P. C.; Offen, H. W. J. Chem. Phys. 1971, 55, 2945.
72. Klӧpffer, W. J. Chem. Phys. 1969, 50, 2337.
73. Klӧpffer, W.; Bunsenges, Ber. Chem. Phys. 1969, 73, 864.
74. Yin, X. Y.; Ye, C.; Ma, X.; Chen, E. Q.; Qi, X. Y.; Duan, X. F.; Wan, X. H.; S. Cheng, Z. D.; Zhou, Q. F. J. Am. Chem. Soc. 2003, 125, 6854.
75. Nakano, T.; Yade, T. J. Am. Chem. Soc. 2003, 125, 15474.
76. Rathore, R.; Abdelwahed, S. H.; Guzei, I. A. J. Am. Chem. Soc. 2003, 125, 8712.
77. Lin, H. –C.; Chu, H. –C.; Lee, Y. –H.; Hsu, S. –J.; Yang, P. –J.; Yabushita, A. J. Phys. Chem. B 2011, 115,8845.
78. Hong, J. L.; Lai, C. T. J. Phys. Chem. B 2010, 114, 10302.
79. Natta, G.; Pino, P.; Corradini, P.; Danusso, F.; Mantica, E.; Mazzanti, G.; Moraglio, G. J. Am. Chem. Soc. 1955, 77, 1708.
80. Natta, G.; Pino, P.; Mazzanti, G.; Giannini, U. J. Am. Chem. Soc. 1957, 79, 2975.
81. Lam, J. W. Y.; Tang, B. Z.; J. Polym. Sci. Part A: Polym. Chem. 2003, 41, 2607.
82. Dong, Y.; Lam, J. W. Y.; Peng, H.; Cheuk, K. K. L.; Kwok, H. S.; Tang, B. Z. Macromolecules 2004, 37, 6408.
83. Lam, J. W. Y.; Tang, B. Z. Acc. Chem. Res. 2005, 38, 745.
84. Lam, J. W. Y.; Dong, Y.; Law, C. C. W.; Dong, Y. Q.; Cheuk, K. K. L.; Lai, L. M.; Li, Z.; Sun, J.; Chen, H.; Zheng, Q.; Kwok, H. S.; Wang, M.; Feng, X.; Shen, J.; Tang, B. Z. Macromolecules 2005, 38, 3290.
85. Lam, J. W. Y.; Dong, Y.; Kwok, H. S.; Tang, B. Z. Macromolecules 2006, 39, 6997.
86. Qin, A.; Jim, C. K. W.; Tang, Y.; Lam, J. W. Y.; Liu, J.; Mahtab, F.; Gao, P.; Tang, B. Z. J. Phys. Chem. B 2008, 112, 9281.