具潛在光電性質之環苯雙烯衍生物及其高分子之合成與鑑定

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研究生：	賴郁淳 Yu-Chun Lai
論文名稱：	具潛在光電性質之環苯雙烯衍生物及其高分子之合成與鑑定 Synthesis and Characterization of Cyclophanediene Derivatives and Their Polymers for Potential Uses in Optoelectronics
指導教授：	游進陽 Chin-Yang Yu
口試委員:	陳志堅 Jyh-Chien Chen 堀江正樹 Masaki Horie
學位類別：	碩士 Master
系所名稱：	工程學院 - 材料科學與工程系 Department of Materials Science and Engineering
論文出版年：	2018
畢業學年度：	106
語文別：	英文
論文頁數：	109
中文關鍵詞：	環苯雙烯、四苯乙烯、聚集誘導發光、開環歧化聚合、聚對苯乙烯
外文關鍵詞：	[2.2]paracyclophane-1,9-diene, tetraphenylethylene, aggregation-induced emission, ring-opening metathesis polymerization, poly(p-phenylene vinylene)s
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上一筆

在眾多共軛高分子中，聚對苯乙烯(poly(p-phenylene vinylene)s)吸引了很大部分的關注與研究，良好的光電性質讓聚對苯乙烯衍生物們成為光電元件材料的熱門選擇，然而，受到聚集螢光淬滅效應(Aggregation-caused quenching)的影響，聚對苯乙烯衍生物的螢光在固體時會大幅下降進而限制了應用上的發展；相反地，四苯乙烯為一個具有良好聚集誘導發光(Aggregation-induced emission)性質的分子，換句話說，它在聚集態時會發出強烈的螢光。我們希望經由導入四苯乙烯分子成為高分子的支鏈來改善聚對苯乙烯衍生物的聚集螢光淬滅效應。
本研究成功合成單一聚苯乙烯取代之環苯雙烯，再利用釕系催化劑進行開環歧化聚合反應得到我們預先設想的擁有四苯乙烯取代之聚對苯乙烯。單一聚苯乙烯取代之環苯雙烯與其高分子都進行了光學性質、熱性質的測定，另外高分子也進行電化學性質的檢測並呈現於本論文中。

Poly (p-phenylene vinylene) derivatives have been attracted tremendous studies among conjugated polymers. The favorable optoelectronic properties make PPVs a popular choice in organic electronic devices. However, the poor emission in solid-state, known as aggregation-caused quenching (ACQ), block the further applications of PPVs. On the contrast, tetraphenylethylene (TPE) is an AIE, i.e. aggregation-induced emission, active molecule, which displays highly emission in aggregation state. We expected the introduction of TPE as side groups can improve the ACQ problem.
Here in, TPE-substituted [2.2]paracyclophane-1,9-diene, as a target monomer, has been synthesized and characterized. Followed by ring-opening metathesis polymerization (ROMP) with ruthenium-based catalyst, the expecting tetraphenylethylene substituted PPV can be obtained. Both monomer and polymers showed high fluorescence in solid state. The molecular weights, optical, thermal and electrochemical properties of polymers were investigated and reported in this thesis.

Abstract    I
List of content    II
Chapter 1. Introdution and Aims    1
1 Conjugated polymer    2
2 Synthesis of PPV    3
2.1 Precursor routes to PPVs    3
2.2 Direct routes to PPVs    6
3 Ring-opening metathesis polymerization (ROMP)    7
3.1 Catalysts for ROMP    9
3.2 Poly(p-phenylene vinylene)s through ROMP    10
4 Aggregation-induced emission (AIE)    12
4.1 Mechanistic discussion    14
4.2 Introduction to tetraphenylethylene    16
5 Aims of the project    16
6 References    17
Chapter 2. Previous Studies of Bromo-Substituted Paracyclophanedienes    20
1 Introduction    21
2 Synthesis and characterization of pseudo-dibromo substituted [2.2]paracyclophane-1,9-diene    22
3 Synthesis and characterization of dibromo substituted [2.2]paracyclophane-1,9-diene    30
4 Experimental    35
4.1 Synthesis    36
4.1.1 Synthesis of 2-bromo-1,4-dimethylbenzene (1)    36
4.1.2 Synthesis of 1-bromo-2,5-bis(bromomethyl)benzene (2)    36
4.1.3 Synthesis of 1-bromo-2,5-bis(thiolatomethyl)benzene (3)    37
4.1.4 Synthesis of 6,14-dibromo-2,11-dithia[3.3]paracyclophane, 6,15-dibromo-2,11-dithia[3.3]paracyclophane, 5,18-dibromo-2,11-dithia[3.3]paracyclophane, and 5,17-dibromo-2,11-dithia[3.3]paracyclophane (4)    37
4.1.5 Synthesis of bis(sulfide) compounds (5)    38
4.1.6 Synthesis of bis(sulfoxide) compounds (6)    38
4.1.7 Synthesis of 5,12-dibromo-[2.2]paracyclophane-1,9-diene (7a), 5,13-dibromo-[2.2]paracyclophane-1,9-diene (7b), 4,16-dibromo-[2.2]paracyclophane-1,9-diene (7c), 4,15-dibromo-[2.2]paracyclophane-1,9-diene (7d)    38
4.1.8 Synthesis of 1,4-dibromo-2,5-dimethylbenzene (8)    39
4.1.9 Synthesis of 1,4-dbromo-2,5-bis(bromomethyl)benzene (9)    39
4.1.10 Synthesis of 1,4-bis(bromomethyl)benzene (10)    40
4.1.11 Synthesis of 1,4-bis(thiolatomethyl)benzene (11)    40
4.1.12 Synthesis of 5,8-dibromo-2,11-dithia[3.3]paracyclophane (12)    41
1.1.13 Synthesis of bis(sulfide) compounds (13)    41
4.1.14 Synthesis of bis(sulfoxide) compounds (14)    41
4.1.15 Synthesis of 4,7-dibromo-[2.2]paracyclophane-1,9-diene (15)    42
5 Summary    42
6 References    43
Chapter 3. Synthesis and Characterization of Monomer – TPE Substituted [2.2]Paracyclophane-1,9-diene    44
1 Introduction    45
2 Results and discussion    46
2.1 Optical properties    54
2.2 Thermal properties    57
3 Experimental    57
3.1 Synthesis    58
3.1.1 Synthesis of 5-bromo-2,11-dithia[3.3]paracyclophane (16)    58
3.1.2 Synthesis of bis(sulfide) compounds (17)    59
3.1.3 Synthesis of bis(sulfoxide) compounds (18)    59
3.1.4 Synthesis of 4-bromo-[2.2]paracyclophane-1,9-diene (19)    60
3.1.5 Synthesis of 4-(4-(1,2,2-triphenylvinyl)phenyl)-[2.2]paracyclophane-1,9-diene (20)    60
4 Summary    61
5 References    62
Chapter 4. Preparation and Characterization of Phenylenevinylene Homopolymers via ROMP    63
1 Introduction    64
2 Results and Discussion    66
2.1 Molecular weight and structure characterization    67
2.2 Optical properties    68
2.3 Thermal properties    74
2.4 Electrochemical properties    74
3 Experimental    76
3.1 Synthesis    76
3.1.1 Synthesis of poly (p-phenylenevinylene-2-(4-(1,2,2-triphenylvinyl)phenyl)-p-phenylenevinylene)s (P1-P3)    76
4 Summary    77
5 References    77
Chapter 5. Conclusion    79
Appendix    81
1H, 13C, and COSY NMR spectra    82
Mass spectroscopy    91
Crystal data and structure refinement    101


                                

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