非共平面芳香族發光體可藉由抑制分子內轉動(restricted intramolecular rotation, RIR)進而顯現聚集發光增強效應(aggregation-enhanced emission, AEE),增強RIR現象之方式，除利用巨大基團限制分子轉動外，結晶亦可限制分子轉動。在第一章裡，含有鄰位和對位羥基基團的有機螢光分子CN4OH，其發光效率與結晶度有關，將螢光分子CN4OH藉由氫鍵作用力與PVP混摻，當混摻1當量或2當量的PVP時其固體發光效率遠遠大於純的螢光分子CN4OH，由WAXD也可看出隨著PVP混摻的量增加其結晶度隨著增加，此時我們認為是與對位的羥基形成氫鍵作用力，隨後再將PVP混摻的量增加到4當量，因為開始與鄰位的羥基產生氫鍵鍵結而無法形成真正放光的form(Enol form→Keto form)，因此發光效率下降，而我們也由WAXD發現其結晶度下降，由實驗結果來看此分子其發光是受結晶而有所影響的，證明此螢光分子CN4OH是一個Crystallization- Enhanced Emission (CEE) 的材料。
當混摻PVP的量增加至2當量時(CN4OH/PVP = 2/1)，由WAXD可看出結晶度提升，其有可能是因為結晶的關係限制分子轉動造成發光效率提升，而當混摻PVP的量增加至4當量時(CN4OH/PVP = 1/1)，由於PVP與鄰位的羥基基團形成氫鍵進而破壞螢光分子的結晶，由WAXD也可看出結晶度下降，因此導致發光效率下降，然而，當混摻適當PVP的量，形成氫鍵的相互作用力，其發光效率可高達88%。
在第二章裡，我們合成了以希夫鹼為中心的PLLA高分子，首先我們先做了兩組不同分子量的高分子，由WAXD可觀察到不同分子量具有不同結晶度，再用螢光光譜儀去觀察其不同結晶度對於放光的影響。之後利用熱處理製作Amorphous film並與Crystalline film比較，發現Amorphous film的發光較弱，有可能是結晶度影響了發光，之後將Amorphous film做solvent annealing後發現發光隨著fuming時間增加強度逐漸增強，並由WAXD光譜可看出結晶度明顯的改善，代表此CN-PLLA(n)s 高分子具有結晶增強放光性質。

Restricted intramolecular rotation (RIR) of the non-coplanar aromatic fluorophores has been proven in several instances as the operative mechanism leading to the aggregation-enhanced emission (AEE) property. Besides using the bulky substituent as structural moiety of AEE-active materials, crystallization is also considered to be effective in reinforcing RIR. In chapter 1, An organic azine derivative of CN4OH, containing both of the para- and the ortho-hydroxyl (p- and o-OH) groups, is a fluorescent material with its emission efficiency dependent on the degree of crystallinity. With inherent hydroxyl groups, CN4OH can be homogeneously blended with different amounts of poly(4-vinyl pyridine) (PVP) through intermolecular hydrogen-bond (H-bond) interactions. With the incorporations of one and two molar equivalents of PVP, the solid CN4OH/PVP(4/1) and (2/1) blends emit strongly with intensity larger than the pure CN4OH. Nevertheless, further increase of the PVP content considerably reduced the crystallinity and the emission efficiency of the blend. Initially, PVP was preferably H-bonded to the p-OHs of CN4OH, resulting in the beneficial crystallization-enhanced emission (CEE); nevertheless, the PVP added in the later step started to bond to the o-OHs of CN4OH, reducing the crystallinity and the CEE-related fluorescence. With appropriate H-bond interaction, the CN4OH/PVP(2/1) blend emits with a high quantum yield (ɸF) of 88%, in contrast to the low ɸF of 15% for pure CN4OH. In chapter 2, Polymeric luminogen with Aggregation-enhanced emission (AEE) and crystallization-enhanced emission (CEE) behavior was prepared and characterized in this study. Schiff-base polymeric luminogen was prepared via the ring opening polymerization. First, we synthesized different molecule weight of Polymeric luminogen to observed crystallinity relative emission impact. Then the emission behavior of the CN-PLLA(n)s in heat treatment and solvent annealing was shown to correlate with CEE behavior, We was prepared a amorphous film by heat treatment then comparison with crystalline film, the crystal film emission is better than amorphous film. Then we will amorphous film do solvent annealing, after solvent fuming process, we check WAXD. In WAXD, have displays sharp reflection peaks and emission was gradually enhanced with increasing exposure time. Therefore, CN-PLLA(n)s is a fluorophore with CEE character.

Outline of Contents
Chinese Abstract...................................................................................................................................i
English Abstract................................................................................................................................... ii
Outline of Contents............................................................................................................................... iv
List of Figure......................................................................................................................................... vi
List of Scheme..................................................................................................................................... x
List of Table.......................................................................................................................................... x
Chapter 1
Crystallization-enhanced emission through hydrogen-bond interactions in blends containing hydroxyl-functionalized azine and poly(4-vinyl pyridine).................................................................................. - 1 -
1-1-1. Crystallization-enhanced emission (CEE)............................................................................. - 1 -
1-1-2. Hydrogen Bonds to enhance aggregation emission............................................................ - 3 -
1-1-3. Hydrogen Bonds to crystalline-induced emission (CIE)....................................................... - 9 -
1-2. Materials....................................................................................................................................... - 16 -
1-3. Instrumentation............................................................................................................................. - 16 -
1-4. Synthesis of 1,2-bis(2,4-dihydroxybenzylidene)hydrazine (CN4OH) and 2,2-bis(2-hydroxybenzylidene)hydrazine (CN2OH)........................................................................................... - 17 -
1-5. Results and discussion................................................................................................................ - 19 -
1-5-1. Emission behavior of CN4OH................................................................................................. - 19 -
1-5-2. Blending of CN4OH with PVP................................................................................................ - 24 -
1-6. Conclusion.................................................................................................................................... - 36 -
1-7. References................................................................................................................................... - 37 -
Chapter 2
Crystallization-enhanced emission of poly(L-lactide) terminated with a azine fluorescent center - 40 -
2-1-1 Aggregation-Induced Emission (AIE)...................................................................................... - 40 -
2-1-2 Crystallization-Induced Emission Enhancement.................................................................... - 42 -
2-1-3. Poly(L-lactide)........................................................................................................................... - 43 -
2-2. Materials........................................................................................................................................ - 49 -
2-3. Instrumentation.............................................................................................................................. - 49 -
2-4. Preparation of polymers by ring opening polymerization (ROP)............................................. - 50 -
2-5. Results and discussion................................................................................................................ - 52 -
2-5-1. Aggregation-enhanced emission of CN-PLLA(n)s............................................................... - 55 -
2-5-2. Crystallization-promoted emission in the solid CN-PLLA(n)s............................................. - 61 -
2-5-3. Thermal treatment and solvent annealing............................................................................... - 62 -
2-5-4. Comparison between polymeric and monomeric fluorophores........................................... - 66 -
2-6. Conclusion.................................................................................................................................... - 67 -
2-7. References................................................................................................................................... - 68 -
Supporting information........................................................................................................................ - 70 -

Chapter 1
1. Y. Dong, J. W. Y. Lam, A. Qin, J. Sun, J. Liu, Z. Li, J. Sun, H. H. Y. Sung, I. D. Williams, H. S. Kwokc, B. Z. Tang, Chem. Commun. 2007, 3255.
2. Wei-Lun Chien, Chih-Min Yang, Tai-Lin Chen, Shu-Ting Li and Jin-Long Hong, RSC Adv., 2013,3, 6930-6938
3. J. Liu, J. W. Y. Lam and B. Z. Tang, J. Inorg. Organomet. Polym. Mater, 2009, 19, 249.
4. J. Luo, Z. Xie, J. W. Y. Lam, L. Cheng, H. Chen, C. Qiu, H. S. Kwok, X. Zhan, Y. Liu, D. Zhu and B. Z. Tang, Chem. Commun., 2001, 1740.
5. B. Z. Tang, X. Zhan, G. Yu, P. P. S. Lee, Y. Liu and D. Zhu, J. Mater. Chem., 2001, 11, 2974.
6. Aggregation-Induced Emission: Fundamentals
7. Y. Hong, J. W. Y. Lam and B. Z. Tang, Chem. Commun., 2009, 4332.
8. J. Wu, W. Liu, J. Ge, H. Zhang and P. Wang, Chem. Soc. Rev., 2011, 40, 3483.
9. Y. Hong, J. W. Y. Lam and B. Z. Tang, Chem. Soc. Rev., 2011, 40, 5361.
10. A. Qin, J. W. Y. Lam and B. Z. Tang, Prog. Polym. Sci., 2012, 37, 182.7.
11. J. Chen, C. C. W. Law, J. W. Y. Lam, Y. Dong, S. M. F. Lo, I. D. Williams, D. Zhu and B. Z. Tang, Chem. Mater., 2003, 15, 1535.
12. B. Z. Tang, Y. Geng, J. W. Y. Lam, B. Li, X. Jing, X. Wang, F. Wang, A. B. Pakhomov and X. Zhang, Chem. Mater., 1999, 11, 1581.
13. Z. Li, Y. Dong, B. Mi, Y. Tang, M. Haeussler, H. Tong, Y. Dong, J. W. Y. Lam, Y. Ren, H. H. Y. Sung, K. S. Wong, P. Gao, I. D. Williams, H. S. Kwok and B. Z. Tang, J. Phys. Chem. B, 2005, 109, 10061.
14. Y. Dong, J. W. Y. Lam, A. Qin, J. Sun, J. Liu, Z. Li, J. Sun, H. H. Y. Sung, I. D. Williams, H. S. Kwok and B. Z. Tang, Chem. Commun, 2007, 3255.
15. Y. Dong, J. W. Y. Lam, A. Qin, J. Liu, Z. Li, B. Z. Tang, J. Sun and H. S. Kwok, Appl. Phys. Lett., 2007, 91, 011111.
16. H. Tong, Y. Dong, M. Haeussler, J. W. Y. Lam, H. H. Y. Sung, I. D. Williams, J Sun and B. Z. Tang, Chem. Commun., 2006, 1133.
17. Y. Dong, J. W. Y. Lam, A. Qin, Z. Li, J. Sun, H. H. Y. Sung, I. D. Williams and B. Z. Tang, Chem. Commun., 2007, 40.
18. H. Tong, Y. Dong, Y. Hong, M. Haeussler, J. W. Y. Lam, H. H. Y. Sung, X. Yu, J. Sun, I. D. Williams, H. S. Kwok and B. Z. Tang, J. Phys. Chem. C, 2007, 111, 2287.
19. Y. Liu, X. Tao, F. Wang, J. Shi, J. Sun, W. Yu, Y. Ren, D. Zou and M. Jiang, J. Phys. Chem. C, 2007, 111, 6544.
20. P. Chen, R. Lu, P. Xue, T. Xu, G. Chen and Y. Zhao, Langmuir, 2009, 25, 8395.
21. P. Zhang, H. Wang, H. Liu and M. Li, Langmuir, 2010, 26, 10183.
22. T. H. Kim, M. S. Choi, B. H. Sohn, S. Y. Park, W. S. Lyoo and T. S. Lee, Chem. Commun., 2008, 2364.
23. J. H. Wan, L. Y. Mao, Y. B. Li, Z. F. Li, H. Y. Qiu, C. Wang and G. Q. Lai, Soft Matter, 2010, 6, 3195.
24. M. K. Nayak, J. Photochem. Photobiol., A, 2011, 217, 40.
25. R. H. Chien, C. T. Lai and J. L. Hong, J. Phys. Chem. C, 2011, 115, 12358.
26. S. L. Deng, T. L. Chen, W. L. Chien and J. L. Hong, J. Mater. Chem. C, 2014, 2,651
27. G. Q. Yang, F. Morlet-Savary, Z. K. Peng, S. K. Wu and J. P. Fouassier, Chem. Phys. Lett., 1996, 256, 536.
28. Z. M. Li and S. K. Wu, J. Fluoresc., 1997, 7, 237.
29. P. F. Wang and S. K. Wu, J. Photochem. Photobiol, A, 1995, 86, 109.
30. J. S. Wu, W. M. Liu, X. Q. Zhuang, F. Wang, P. F. Wang, S. L.Tao, X. H. Zhang, S. K. Wu and S. T. Lee, Org. Lett., 2007, 9, 33.
31. W. M. Liu, L. W. Xu, R. L. Sheng, P. F. Wang, H. P. Li and S. K. Wu, Org. Lett., 2007, 9, 3829.
32. D. Ray and P. K. Bharadwaj, Inorg. Chem., 2008, 47, 2252.
33. J. R. Sheng, F. Feng, Y. Qiang, F. G. Liang, L. Sen and F. H. Wei, Anal. Lett., 2008, 41, 2203.
34. Z. X. Li, M. M. Yu, L. F. Zhang, M. Yu, J. X. Liu, L. H. Wei and H. Y. Zhang, Chem. Commun., 2010, 46, 7169.
35. V. Chandrasekhar, P. Bag and M. D. Pandey, Tetrahedron, 2009, 65, 9876.
36. H. S. Jung, K. C. Ko, J. H. Lee, S. H. Kim, S. Bhuniya, J. Y. Lee, Y. Kim, S. J. Kim and J. S. Kim, Inorg. Chem., 2010, 49, 8552.
37. N. Zhao, Y. H. Wu, R. M. Wang, L. X. Shi and Z. N. Chen, Analyst, 2011, 136,2277.
38. N. Zhao, Y. H. Wu, J. Luo, L. X. Shi, and Z. N. Chen, Analyst, 2013, 138, 894.
39. L. Qian, B. Tong, J. Shen, J. Shi, J. Zhi, Y. Dong, F. Yang, Y. Dong, J. W. Y. Lam, Y. Liu and B. Z. Tang, J. Phys. Chem. B, 2009, 113, 9098.
40. C. M. Yang, I. W. Lee, T. L. Chen, W. L. Chien and J. L. Hong, J. Mater. Chem. C, 2013, 1, 2842.

Chapter 2
1. J. D. Luo, Z. Xie, J. W. Y. Lam, L. Cheng, H. Chen, C. Qiu, H. S. Kwok, X. Zhan, Y. Liu, D. Zhu and B. Z. Tang, Chem. Commun, 2001, 1740.
2. B. Z. Tang, X. Zhan, G. Yu, P. P. S. Lee, Y. Liu and D. Zhu, J. Mater. Chem, 2001, 11, 2974.
3. Lijun Qian, Bin Tong, Jinbo Shen, Jianbing Shi, Junge Zhi, Yongqiang Dong, Fan Yang, Yuping Dong , Jacky W. Y. Lam, Yang Liu, and Ben Zhong Tang, J. Phys. Chem. B, 2009, 113, 9098–9103
4. Asutosh Kumar Pandey, Advanced materials letters, 2013, 6489
5. Ray E. Drumright, Patrick R. Gruber,* and David E. Henton, Adv. Mater. 2000, 12, 1841
6. David E. Henton, Patrick Gruber, Jim Lunt, and Jed Randall, Polylactic Acid Technology, 2005, 527
7. A. C. Grimsdale, K. Müllen, Adv. Polym. Sci. 2008, 212, 1.
8. W. W. H. Wong, A. B. Holmes, Adv. Polym. Sci. 2008, 212, 85.
9. P. L. T. Boudreault, N. Blouin, M. Leclerc, Adv. Polym. Sci. 2008, 212, 99.
10. J. C. Sanchez, W. C. Trogler, Macromol. Chem. Phys. 2008, 209, 1527.
11. Y. Zhang, B. Liu, Y. Cao, Chem.–Asian J. 2008, 3, 739.
12. K. Kokado, Y. Chujo, Macromolecules 2009, 42, 1418.K.
13. J. Dong, K. M. Solntsev, L. M. Tolbert, J. Am. Chem. Soc. 2009, 131, 662.
14. W. Tang, Y. Xiang, A. Tong, J. Org. Chem. 2009, 74, 2163.
15. H. Yao, M. Yamashita, K. Kimura, Langmuir 2009, 25, 1131.
16. K.-Y. Pu, B. Liu, Adv. Funct. Mater. 2009, 19, 277.
17. M. Wang, D. Zhang, G. Zhang, D. Zhu, Chem. Commun. 2008, 4469.
18. J. Lv, L. Jiang, C. Li, X. Liu, M. Yuan, J. Xu, W. Zhou, Y. Song, H. Liu, Y. Li, D. Zhu, Langmuir 2008, 24, 8297.
19. Y. Liu, X. Tao, F. Wang, X. Dang, D. Zou, Y. Ren, M. Jiang, J. Phys. Chem. C 2008, 112, 3975.
20. R. Davis, N. S. S. Kumar, S. Abraham, C. H. Suresh, N. P. Rath, N. Tamaoki, S. Das, J. Phys. Chem. C 2008, 112, 2137.
21. Q. Zhao, L. Li, F. Li, N. Yu, Z. Liu, T. Yi, C. Huang, Chem. Commun. 2008, 685.
22. Z. Ning, Z. Chen, Q. Zhang, Y. Yan, S. Qian, Y. Cao, H. Tian, Adv. Funct. Mater. 2007, 17, 3799.
23. D. Yan, J. Mohsseni-Ala, N. Auner, M. Bolte, J. W. Bats, Chem.–Eur. J. 2007, 13, 7204.
24. Y. Qian, S. Li, G. Zhang, Q. Wang, S. Wang, H. Xu, C. Li, Y. Li, G. Yang, J. Phys. Chem. B 2007, 111, 5861.
25. S. Kim, T. Y. Ohulchanskyy, H. E. Pudavar, R. K. Pandey, P. N. Prasad, J. Am. Chem. Soc. 2007, 129, 2669.
26. Y. Li, F. Li, H. Zhang, Z. Xie, W. Xie, H. Xu, B. Li, F. Shen, L. Ye, M. Hanif, D. Ma, Y. Ma, Chem. Commun. 2007, 231.
27. L. Qian, J. Zhi, B. Tong, F. Yang, W. Zhao, Y. Dong, Prog. Chem. (Beijing, China) 2008, 20, 673.
28. T. Baumgartner, R. Reau, Chem. Rev. 2006, 106, 4681.
29. C. J. Bhongale, C. S. Hsu, Angew. Chem. Int. Ed. 2006, 45, 1404.
30. Y. Sun, J. Liao, J. Fang, P. Chou, C. Shen, C. Hsu, L. Chen, Org. Lett. 2006, 8, 3713.
31. Robson F. Storey* and John W. Sherman, Macromolecules 2002, 35, 1504 – 1512
32. H. Tsuji, Y. Ikada b, Polymer 40 (1999) 6699–6708
33. L. Qian, B. Tong, J. Shen, J. Shi, J. Zhi, Y. Dong, F. Yang, Y. Dong, J. W. Y. Lam, Y. Liu, B. Z. Tang, J. Phys. Chem. B 2009, 113, 9098.