二芳基乙烯為近年來廣為研究的分子結構，特殊的光致變色性質為其最大的特色。其中，照光所影響的不只有外觀顏色，共軛與電子結構的改變造成的物理化學變化如分子長度與導電度，亦受眾多研究者關注。不同的官能基帶來不同的光致變化，此有趣的現象擴大了分子應用的範圍，光致共振結構改變也使其被應用在共軛高分子的領域。我們的研究主題為利用麥克默里反應合成含有二芳基乙烯的共軛環狀化合物，並針對其光學性質和單晶結構作特徵分析，再利用此環狀化合物進行開環聚合製造共軛高分子，進行光學特性之分析。此外，我們也致力於合成共軛直鏈狀化合物，以便與高分子作性質比較。
第一章主要介紹光致變色化合物與共軛高分子的基本特性，以及二者主要應用之層面，如光學儲存裝置與有機場效電晶體。此段著重於二芳基乙烯化合物的介紹，講述在眾多光致變色的化合物中，我們選擇二芳基乙烯化合物做為研究對象的契機，以及我們在合成中所使用的反應機制之介紹。
第二章將詳細說明我們的實驗方法與分析結果，觀測反應產物之光致變色與其他性質之改變。實驗內容包含共軛單體與高分子之合成，並進行產物之性質分析與研究，主要著重於可見光吸收光譜、外觀變化與單晶結構。
第三章與第四章講述此實驗之結論與未來的研究方向，而第五章包含詳細的實驗步驟與光譜分析。

Diarylethene derivatives have been widely investigated in recent studies, because of their specific photochromic features and the transformation in molecular length and conductivity upon photoirradiation. Such interesting features have also been introduced into conjugated polymers. In this work, we have synthesized multiple conjugated molecules comprising diarylethene. The cyclic molecules are used for the synthesis of the conjugated polymers via ring-opening metathesis polymerization (ROMP). For comparison, linear conjugated molecules have also been synthesized. Analysis of their photochemical/mechanical properties afterward is also a main study in the work.
In Chapter 1, photochromic molecules and reported conjugated molecules are introduced. In addition, their applications such as optical memory storage and organic field-effect transistors (OFETs) are described. Following is the introduction to reaction mechanism used in this work.
In Chapter 2, the synthesis and analysis of cyclic/linear conjugated molecules and polymers comprising diarylethene are described. They were characterized by UV-vis, 1H NMR, HRFD mass spectroscopies and single-crystal X-ray crystallography.
In Chapters 3 and 4, conclusion of our work and future development are described. In Chapter 5, detailed synthesis procedure, 1H NMR, and HRFD-MS spectra of the products are shown.

中文摘要 I
Abstract II
Chapter 1 Introduction 5
1-1 Introduction to diarylethene 5
1-1-1 Photochromic molecules 5
1-1-2 Diarylethene derivatives and their properties 6
1-1-3 Conjugated molecules comprising diarylethene 12
1-1-3-1 Cyclic conjugated molecules comprising diarylethene 12
1-1-3-2 Advanced diarylethene-containing conjugated polymers 18
1-2 Applications of diarylethene derivatives 21
1-2-1 Optical memory storage of photochromic molecules 21
1-2-2 Organic field-effect transistors based on conjugated polymers 26
1-3 Introduction to synthesis methods 29
1-3-1 McMurry reactions 29
1-3-2 Ring-Opening Metathesis Polymerization (ROMP) 30
1-3-2-1 Olefin metathesis 30
1-3-2-2 Mechanism of ROMP 31
1-3-2-3 Catalysts for living polymerization ROMP 33
1-3-2-4 Reported polymerization via ROMP 37
1-4 Aim of work 42
Chapter 2 Synthesis of monomers and polymers 45
2-1 Synthesis of monomers 45
2-1-1 Synthesis of 3,3’-(1-cyclopentene-1,2-diyl)bis[2-methyl-5-thiophenecarboxaldehyde] 46
2-1-2 Synthesis of cyclic conjugated monomers 47
2-1-3 Synthesis of linear conjugated monomers 54
2-2 Synthesis of polymers 58
2-3 Optical properties of monomers in solid/solution states 61
2-3-1 Optical properties of 3 and 3’ in solid/solution states 61
2-3-2 Optical properties of cyclic monomers (Ma) in solution state 63
2-3-3 Optical properties of linear monomers (Mc) in solution state 64
2-3-4 Optical properties of homopolymer in solution state 70
2-4 Photochromic reaction of monomers in single-crystalline phase 75
2-4-1 Photochromic reaction of 3 and 3’ in single-crystalline phase 75
2-4-2 Photochromic reaction of Ma in single-crystalline phase 83
2-4-3 Photochromic reaction of Mc in single-crystalline phase 87
Chapter 3 Conclusion 91
Chapter 4 Future work 94
Chapter 5 Experiment section 96
5-1 General methods 96
5-2 Synthesis of monomers 96
5-2-1 Synthesis of 1,2-bis(5-chloro-2-methyl-3-thienyl)cyclopentene 96
5-2-1-1 Synthesis of 1,5-bis(5-chloro-2-methyl-3-thienyl)-1,5-pentanedione (1) 96
5-2-1-2 Synthesis of 1,2-bis(5-chloro-2-methyl-3-thienyl)cyclopentene (2) 97
5-2-2 Synthesis of cyclic molecules 98
5-2-2-1 Synthesis of 3,3’-(1-cyclopentene-1,2-diyl)bis[2-methyl-5-thiophenecarboxaldehyde] (3) 98
5-2-2-2 Synthesis of Ma, Mb with open-ring form compound 3 98
5-2-2-3 Synthesis of Ma, Mb with closed-ring form compound 3’ 99
5-2-3 Synthesis of linear molecules 100
5-2-3-1 Synthesis of 4-[2-(5-Chloro-2-methyl-3-thienyl)-1-cyclopentenyl]-5-methyl-2-thiophenecarboxaldehyde 100
5-2-3-2 Synthesis of Mc 101
5-2-4 Synthesis of homopolymer 102
References 110

1. Irie, M.; Fukaminato, T.; Matsuda, K.; Kobatake, S. Photochromism of diarylethene molecules and crystals: memories, switches, and actuators. Chem. Rev. 2014, 114 (24), 12174-12277.
2. Irie, M.; Seki, T.; Yokoyama, Y., New frontiers in photochromism. Springer: 2013.
3. Finkelmann, H.; Nishikawa, E.; Pereira, G.; Warner, M. A new opto-mechanical effect in solids. Phys. Rev. Lett. 2001, 87 (1), 015501.
4. Horie, M.; Wang, C.-H. Stimuli-Responsive Dynamic Pseudorotaxane Crystals. Mater. Chem. Front. 2019.
5. Morimoto, M.; Irie, M. Photochromism of diarylethene single crystals: crystal structures and photochromic performance. ChemComm. 2005, (31), 3895-3905.
6. Kobatake, S.; Irie, M. Single-crystalline photochromism of diarylethenes. Bull. Chem. Soc. Jpn. 2004, 77 (2), 195-210.
7. Kobatake, S.; Takami, S.; Muto, H.; Ishikawa, T.; Irie, M. Rapid and reversible shape changes of molecular crystals on photoirradiation. Nature. 2007, 446 (7137), 778.
8. Chen, S.; Chen, L.-J.; Yang, H.-B.; Tian, H.; Zhu, W. Light-triggered reversible supramolecular transformations of multi-bisthienylethene hexagons. J. Am. Chem. Soc. 2012, 134 (33), 13596-13599.
9. Han, M.; Michel, R.; He, B.; Chen, Y. S.; Stalke, D.; John, M.; Clever, G. H. Light‐Triggered Guest Uptake and Release by a Photochromic Coordination Cage. Angew. Chem. Int. Ed. 2013, 52 (4), 1319-1323.
10. 1Jung, I.; Choi, H.; Kim, E.; Lee, C.-H.; Kang, S. O.; Ko, J. Synthesis and photochromic reactivity of macromolecules incorporating four dithienylethene units. Tetrahedron. 2005, 61 (52), 12256-12263.
11. Kawai, T.; Kunitake, T.; Irie, M. Novel photochromic conducting polymer having diarylethene derivative in the main chain. Chem. Lett. 1999, 28 (9), 905-906.
12. 12. Hanazawa, M.; Sumiya, R.; Horikawa, Y.; Irie, M. Thermally irreversible photochromic systems. Reversible photocyclization of 1, 2-bis (2-methylbenzo [b] thiophen-3-yl) perfluorocyclocoalkene derivatives. J. Chem. Soc. 1992, (3), 206-207.
13. Kawai, T.; Koshido, T.; Nakazono, M.; Yoshino, K. Novel photo-memory effect in photoconductivity of conducting polymer containing photochromic dye. Chem. Lett. 1993, 22 (4), 697-700.
14. Russell, J. T., Multi-layered optical data records and playback apparatus. Google Patents: 1978.
15. Kawata, S.; Kawata, Y. Three-dimensional optical data storage using photochromic materials. Chem. Rev. 2000, 100 (5), 1777-1788.
16. Haase, M.; Qiu, J.; DePuydt, J.; Cheng, H. Blue‐green laser diodes. Appl. Phys. Lett. 1991, 59 (11), 1272-1274.
17. Nakamura, S.; Mukai, T.; Senoh, M. Candela‐class high‐brightness InGaN/AlGaN double‐heterostructure blue‐light‐emitting diodes. Appl. Phys. Lett. 1994, 64 (13), 1687-1689.
18. Nakamura, S.; Senoh, M.; Iwasa, N.; Nagahama, S.-I. High-brightness InGaN blue, green and yellow light-emitting diodes with quantum well structures. Jpn. J. Appl. Phys. 1995, 34 (7A), L797-L799.
19. Crowe, D. G. Near-field optical disk recording for very high data density. Appl. Opt. 1991, 30 (31), 4480-4481.
20. Betzig, E.; Trautman, J.; Wolfe, R.; Gyorgy, E.; Finn, P.; Kryder, M.; Chang, C. H. Near‐field magneto‐optics and high density data storage. Appl. Phys. Lett. 1992, 61 (2), 142-144.
21. Jiang, S.; Ichihashi, J.; Monobe, H.; Fujihira, M.; Ohtsu, M. Highly localized photochemical processes in LB films of photo chromic material by using a photon scanning tunneling microscope. Opt. Commun. 1994, 106 (4-6), 173-177.
22. Tsujioka, T.; Harada, T.; Kume, M.; Kuroki, K.; Irie, M. J. O. R. Super-resolution with a photochromic mask layer in an optical memory. Opt. Rev. 1995, 2 (3), 181-186.
23. Tsujioka, T.; Harada, T.; Kume, M.; Kuroki, K.; Irie, M. Theoretical analysis of photon-mode super-resolution optical memory using saturable absorption dye. Opt. Rev. 1995, 2 (4), 225-228.
24. Tsujioka, T.; Kume, M.; Horikawa, Y.; Ishikawa, A.; Irie, M. Super-resolution disk with a photochromic mask layer. Jpn. J. Appl. Phys. 1997, 36 (1S), 526.
25. Irie, M.; Uchida, K.; Eriguchi, T.; Tsuzuki, H. Photochromism of single crystalline diarylethenes. Chem. Lett. 1995, 24 (10), 899-900.
26. Parthenopoulos, D. A.; Rentzepis, P. M. Three-dimensional optical storage memory. Science. 1989, 245 (4920), 843-845.
27. Irie, M., Photo-reactive materials for ultrahigh density optical memory: MITI research and development program on basic technologies for future industries. Elsevier Science Inc.: 1994.
28. Hamano, M.; Irie, M. Rewritable near-field optical recording on photochromic thin films. Jpn. J. Appl. Phys. 1996, 35 (3R), 1764.
29. Sekkat, Z.; Knoll, W. Creation of second-order nonlinear optical effects by photoisomerization of polar azo dyes in polymeric films: theoretical study of steady-state and transient properties. JOSA B. 1995, 12 (10), 1855-1867.
30. Watanabe, O.; Tsuchimori, M.; Okada, A. Two-step refractive index changes by photoisomerization and photobleaching processes in the films of non-linear optical polyurethanes and a urethane–urea copolymer. J. Mater. Chem. 1996, 6 (9), 1487-1492.
31. Egami, C.; Suzuki, Y.; Sugihara, O.; Okamoto, N.; Fujimura, H.; Nakagawa, K.; Fujiwara, H. Third-order resonant optical nonlinearity from trans–cis photoisomerization of an azo dye in a rigid matrix. Appl. Phys. B. 1997, 64 (4), 471-478.
32. Wang, C.; Fei, H.; Yang, Y.; Wei, Z.; Qiu, Y.; Chen, Y. Photoinduced anisotropy and polarization holography in azobenzene side-chain polymer. Opt. Commun. 1999, 159 (1-3), 58-62.
33. Ishikawa, M.; Kawata, Y.; Egami, C.; Sugihara, O.; Okamoto, N.; Tsuchimori, M.; Watanabe, O. Reflection-type confocal readout for multilayered optical memory. Opt. Lett. 1998, 23 (22), 1781-1783.
34. Lilienfeld, J. JE Lilienfeld US Patent, 1 (1930). US patent 1930, 1, 175.
35. Koezuka, H.; Tsumura, A.; Ando, T. Field-effect transistor with polythiophene thin film. Synth. Met. 1987, 18 (1-3), 699-704.
36. Tsumura, A.; Koezuka, H.; Ando, T. J. A. P. L. Macromolecular electronic device: Field‐effect transistor with a polythiophene thin film. Appl. Phys. Lett. 1986, 49 (18), 1210-1212.
37. Arias, A. C.; MacKenzie, J. D.; McCulloch, I.; Rivnay, J.; Salleo, A. Materials and applications for large area electronics: solution-based approaches. Chemical reviews 2010, 110 (1), 3-24.
38. Fukuda, K.; Takeda, Y.; Yoshimura, Y.; Shiwaku, R.; Tran, L. T.; Sekine, T.; Mizukami, M.; Kumaki, D.; Tokito, S. Fully-printed high-performance organic thin-film transistors and circuitry on one-micron-thick polymer films. Nat. Commun. 2014, 5, 4147.
39. Guo, X.; Xu, Y.; Ogier, S.; Ng, T. N.; Caironi, M.; Perinot, A.; Li, L.; Zhao, J.; Tang, W.; Sporea, R. A. Current status and opportunities of organic thin-film transistor technologies. IEEE Trans. Electron Devices 2017, 64 (5), 1906-1921.
40. Gundlach, D. J. Organic electronics: Low power, high impact. Nat. Mater. 2007, 6 (3), 173.
41. Chang, J.; Lin, Z.; Zhang, C.; Hao, Y., Organic Field-Effect Transistor: Device Physics, Materials, and Process. In Different Types of Field-Effect Transistors - Theory and Applications, 2017.
42. Quinn, J. T.; Zhu, J.; Li, X.; Wang, J.; Li, Y. Recent progress in the development of n-type organic semiconductors for organic field effect transistors. J. Mater. Chem. C 2017, 5 (34), 8654-8681.
43. Lakshminarayana, A. N.; Ong, A.; Chi, C. Modification of acenes for n-channel OFET materials. J. Mater. Chem. C 2018, 6 (14), 3551-3563.
44. Horowitz, G. Organic field‐effect transistors. Adv. Mater. 1998, 10 (5), 365-377.
45. Karl, N.; Kraft, K.-H.; Marktanner, J.; Münch, M.; Schatz, F.; Stehle, R.; Uhde, H.-M. Fast electronic transport in organic molecular solids? J. Vac. Sci. Technol. A. 1999, 17 (4), 2318-2328.
46. Hasegawa, T.; Takeya, J. Organic field-effect transistors using single crystals. Sci. Technol. Adv. Mater. 2009, 10 (2), 024314.
47. Lei, T.; Dou, J. H.; Pei, J. Influence of Alkyl Chain Branching Positions on the Hole Mobilities of Polymer Thin‐Film Transistors. Adv. Mater. 2012, 24 (48), 6457-6461
48. Kanimozhi, C.; Yaacobi-Gross, N.; Chou, K. W.; Amassian, A.; Anthopoulos, T. D.; Patil, S. Diketopyrrolopyrrole–Diketopyrrolopyrrole-Based Conjugated Copolymer for High-Mobility Organic Field-Effect Transistors. J. Am. Chem. Soc. 2012, 134 (40), 16532-16535
49. Kang, I.; Yun, H.-J.; Chung, D. S.; Kwon, S.-K.; Kim, Y.-H. Record high hole mobility in polymer semiconductors via side-chain engineering. J. Am. Chem. Soc. 2013, 135 (40), 14896-14899.
50. McMurry, J. E.; Fleming, M. P. New method for the reductive coupling of carbonyls to olefins. Synthesis of. beta.-carotene. J. Am. Chem. Soc. 1974, 96 (14), 4708-4709.
51. Grubbs, R. H.; Chang, S. Recent advances in olefin metathesis and its application in organic synthesis. Tetrahedron 1998, 54 (18), 4413-4450
52. Bielawski, C. W.; Grubbs, R. H. Living ring-opening metathesis polymerization. Prog. Polym. Sci. 2007, 32 (1), 1-29
53. Amir-Ebrahimi, V.; Corry, D.; Hamilton, J.; Thompson, J.; Rooney, J. Characteristics of RuCl2 (CHPh)(PCy3) 2 as a catalyst for ring-opening metathesis polymerization. Macromolecules. 2000, 33 (3), 717-724.
54. Laverty, D. T.; Rooney, J. J. Mechanism of initiation of the ring-opening polymerization and addition oligomerization of norbornene using unicomponent metathesis catalysts. J. Chem. Soc. 1983, 79 (4), 869-878.
55. Trnka, T. M.; Grubbs, R. H. The development of L2X2Ru CHR olefin metathesis catalysts: an organometallic success story. Acc. Chem. Res. 2001, 34 (1), 18-29.
56. Fischer, E.; Maasböl, A. Zur Frage eines Wolfram‐Carbonyl‐Carben‐Komplexes. Angew. Chem. 1964, 76 (14), 645-645.
57. Schrock, R. R. Alkylcarbene complex of tantalum by intramolecular. alpha.-hydrogen abstraction. J. Am. Chem. Soc. 1974, 96 (21), 6796-6797.
58. Bazan, G. C.; Oskam, J. H.; Cho, H. N.; Park, L. Y.; Schrock, R. R. Living ring-opening metathesis polymerization of 2, 3-difunctionalized 7-oxanorbornenes and 7-oxanorbornadienes by Mo (CHCMe2R)(NC6H3-iso-Pr2-2, 6)(O-tert-Bu) 2 and Mo (CHCMe2R)(NC6H3-iso-Pr2-2, 6)(OCMe2CF3) 2. J. Am. Chem. Soc. 1991, 113 (18), 6899-6907.
59. Schwab, P.; Grubbs, R. H.; Ziller, J. W. Synthesis and applications of RuCl2 (CHR ‘)(PR3) 2: the influence of the alkylidene moiety on metathesis activity. J. Am. Chem. Soc. 1996, 118 (1), 100-110.
60. Cucullu, M. E.; Li, C.; Nolan, S. P.; Nguyen, S. T.; Grubbs, R. H. Thermochemical Investigation of Phosphine Ligand Substitution Reactions Involving trans-(PR3) 2Cl2Ru CH− CH CPh2 Complexes. Organometallics. 1998, 17 (25), 5565-5568.
61. Ulman, M.; Grubbs, R. H. Relative reaction rates of olefin substrates with ruthenium (II) carbene metathesis initiators1. Organometallics. 1998, 17 (12), 2484-2489.
62. Ulman, M.; Belderrain, T. R.; Grubbs, R. H. A series of ruthenium (II) ester-carbene complexes as olefin metathesis initiators: metathesis of acrylates. Tetrahedron Lett. 2000, 41 (24), 4689-4693.
63. Bourissou, D.; Guerret, O.; Gabbai, F. P.; Bertrand, G. Stable carbenes. Chem. Rev. 2000, 100 (1), 39-92.
64. Yu, C. Y.; Kingsley, J. W.; Lidzey, D. G.; Turner, M. L. Phenylenevinylene Block Copolymers via Ring‐Opening Metathesis Polymerization. Macromol. Rapid Commun. 2009, 30 (22), 1889-1892.
65. Yu, C. Y.; Turner, M. L. J. A. C. I. E. Soluble Poly (p‐phenylenevinylene) s through Ring‐Opening Metathesis Polymerization. Angew. Chem. 2006, 45 (46), 7797-7800.
66. Spring, A. M.; Yu, C.-Y.; Horie, M.; Turner, M. L. MEH-PPV by microwave assisted ring-opening metathesis polymerisation. ChemComm. 2009, (19), 2676-2678.
67. Yu, C.-Y.; Horie, M.; Spring, A. M.; Tremel, K.; Turner, M. L. Homopolymers and Block Copolymers of p-Phenylenevinylene-2, 5-diethylhexyloxy-p-phenylenevinylene and m-Phenylenevinylene-2, 5-diethylhexyloxy-p-phenylenevinylene by Ring-Opening Metathesis Polymerization. Macromolecules. 2009, 43 (1), 222-232.
68. Lidster, B. J.; Kumar, D. R.; Spring, A. M.; Yu, C.-Y.; Turner, M. L. Alkyl substituted poly (p-phenylene vinylene)s by ring opening metathesis polymerisation. Polym. Chem. 2016, 7 (35), 5544-5551.
69. Yamada, Y.; Nakamura, T.; Yano, K. In situ green synthesis of fluorescent monodispersed mesoporous silica spheres/poly (p-phenylenevinylene) composites. J. Colloid Interface Sci. 2016, 468, 292-299.
70. Xiong, L.; Cao, F.; Cao, X.; Guo, Y.; Zhang, Y.; Cai, X. Long-term-stable near-infrared polymer dots with ultrasmall size and narrow-band emission for imaging tumor vasculature in vivo. Bioconjugate Chem. 2015, 26 (5), 817-821.
71. Grimsdale, A. C.; Leok Chan, K.; Martin, R. E.; Jokisz, P. G.; Holmes, A. B. Synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Chem. Rev. 2009, 109 (3), 897-1091.
72. Kraft, A.; Grimsdale, A. C.; Holmes, A. B. Electroluminescent conjugated polymers—seeing polymers in a new light. Angew. Chem. Int. Ed. 1998, 37 (4), 402-428.
73. Lidster, B. J.; Behrendt, J. M.; Turner, M. L. Monotelechelic poly (p-phenylenevinylene) s by ring opening metathesis polymerisation. ChemComm. 2014, 50 (80), 11867-11870.
74. Yu, C. Y.; Lai, Y. C. Soluble Phenylenevinylene Polymers Containing Tetraphenylethene Units by Ring‐Opening Metathesis Polymerization. Macromol. Chem. Phys. 2018, 219 (16), 1800135.
75. Chang, S. W.; Horie, M. A donor-acceptor conjugated block copolymer of poly(arylenevinylene)s by ring-opening metathesis polymerization. ChemComm. 2015, 51 (44), 9113-6.
76. Yamaguchi, T.; Hosaka, M.; Shinohara, K.; Ozeki, T.; Fukuda, M.; Takami, S.; Ishibashi, Y.; Asahi, T.; Morimoto, M. Photochromism and Fluorescence Properties of 1, 2-Bis (2-alkyl-1-benzothiophene-3-yl) perhydrocyclopentenes. J. Photochem. Photobiol, A 2014, 285, 44-51.