含四苯乙烯小分子衍生物與高分子合成及性質鑑定｜國立臺灣科技大學博碩士論文系統

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研究生：	徐嘉杰 Chia-Chieh Hsu
論文名稱：	含四苯乙烯小分子衍生物與高分子合成及性質鑑定 Synthesis and Characterization of Small Molecules and Polymers Based on Tetraphenylethene Derivatives
指導教授：	游進陽 Chin-Yang Yu
口試委員:	王承浩 Chen-Hao Wang 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：	132
中文關鍵詞：	四苯乙烯、[2.2]對環芳烷、聚集誘導發光、氟化、機械致螢光變色
外文關鍵詞：	tetraphenylethene, [2.2]paracyclophane, aggregation-induce emission, fluorination, mechanochromism
相關次數：	點閱：375 下載：0
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上一筆

本論文主要探討共軛高分子與共軛分子含有四苯乙烯分子的合成與性質探討。前者共軛高分子為[2.2]對環芳烷與四苯乙烯所形成交替共聚物，後者為D-A-D共軛分子(D為四苯乙烯，A為苯並噻二唑)。相較於傳統的螢光分子，四苯乙烯分子與其衍生物具有聚集誘導發光，此類型螢光材料在固體狀態可產生高強度螢光。所選用的高分子聚合反應為鈴木偶合反應，透過一系列的反應條件中，我們發現鹼的濃度與鈀金屬催化劑的選擇對於合成高分子有一定程度的影響。所合成的高分子具有高強度綠色熒光而添加二硝基甲苯可導致其螢光消光。
部份四苯乙烯分子的衍生物在不同的固體結構可以產生不同顏色的螢光，在這裡我們合成氟原子取代苯並噻二唑將導致鈴木偶合反應效率下降。我們所合成具有聚集誘導發光性質的氟取代衍生物在經過熱處理前後形成明顯的螢光顏色差異。

This thesis presents the synthesis and properties of novel conjugated polymers containing [2.2]paracyclophane and tetraphenylethene and donor-acceptor-donor type of conjugated molecules containing benzothiadiazole and tetraphenylethene. Compared with conventional fluorescent materials, new materials containing tetraphenylethene exhibited high emission in the solid state, well-known aggregation-induced emission. According a series of reaction conditions, we found base and catalyst could optimize the polymerization. These two-dimension conjugated polymers are green fluorescence and DNT could quench its fluorescence in the solid state.
Particularly, the emission color of tetraphenylethene derivatives is highly depends on its structure mode in the solid. Here, we choose incorporation fluorine atom to build novel fluorescent materials. Fluorinated substitution benzothiadiazole could decrease efficiency of Suzuki cross-coupling reaction. These fluorinated fluorescent materials display high color contrast in the solid state by thermal stimulus.

Table of content
Table of content    II
Abstract    VI
中文摘要    VII
Acknowledgements    VIII
Chapter 1. Introduction and aim    1
1 Introduction to conjugated polymers    2
1.1 π-Conjugated materials    2
1.2 π-Conjugated polymers    3
1.3 Band gap of conjugated polymer    4
2 Introduction to π stacked polymers    5
2.1 π Stacked polymers    5
2.2 [2,2]Paracyclophane    6
2.3 [2.2]Paracyclophane-based conjugated polymers    8
3 Introduction to aggregation-induced emission    11
3.1 Restriction of Intermolecular Rotation    12
3.2 Chemosensors    14
4 Aim of project    16
Chapter 2. Results and Discussion    17
1 Synthesis and characterization    18
1.1 Synthesis and characterization of monomers    18
1.2 Synthesis and characterization of precursors    22
1.3 Synthesis and characterization of target molecules    25
1.4 Synthesis and characterization of model compound and target polymers    28
2 Properties    33
2.1 Optical properties to target molecules    33
2.2 Optical properties to model compound and polymers    35
2.3 Electrochemical properties to target polymers    38
2.4 Thermal properties    39
3 Explosive detection    41
3.1 Explosive detection in the solution    41
3.2 Explosive detection in the solid state    43
Reference    45
Chapter 3. Result and Discussion    49
1. Introduction to Mechanochromism    50
1.1 Mechanochromic materials    50
1.2 Donor-Acceptor molecules    51
2 Synthesis and characterization    54
2.1 Synthesis and characterization of precursors    54
2.2 Synthesis and characterization of target molecules    58
3 Properties    60
3.1 Optical properties to target molecules    60
3.2 Structure relationship of target molecules    64
3.3 Thermal properties to target molecules    68
4 Solvatochromism behavior    70
5 Mechanochromism behavior    72
Reference    75
Chapter 4. Conclusion    78
1 Conclusions    79
Chapter 5. Experimental    80
1 General procedure    81
2 Synthesis of monomers    82
2.1 Synthesis of pseudo-para-dibromo[2,2]paracyclophane    82
2.2 Synthesis of pseudo-meta-dibromo[2,2]paracyclophane    83
2.3 Synthesis of (E,Z) 1,2-bis(4-bromophenyl)-1,2-diphenylethene    83
2.4 Synthesis of (E,Z) 1,2-diphenyl-1,2-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethene    84
3 Synthesis of precursors, model compound    85
3.1 Synthesis of 1-(4-Bromophenyl)-1,2,2-triphenylethylene    85
3.2 Synthesis of 4,4,5,5-tetramethyl-2-(4-(1,2,2-triphenylvinyl) phenyl)-1,3,2-dioxaborolane    86
3.3 Synthesis of (E,Z) 1,2-di([1,1'-biphenyl]-4-yl)-1,2-diphenylethene    87
4 Synthesis of target molecules    88
4.1 Synthesis of pseudo-para-bis(4-(1,2,2-triphenylvinyl)phenyl) [2,2]paracyclophane    88
4.2 Synthesis of pseudo-para-bis(4-(1,2,2-triphenylvinyl)phenyl) [2,2]paracyclophane    89
5 Synthesis of target polymers    90
5.1 A typical procedure using Pd(PPh3)4 as catalyst    90
5.2 A typical procedure using Pd(OAc)2 as catalyst    91
6 Synthesis of precursors and target molecules    92
6.1 Synthesis of 5-fluorobenzo[c][1,2,5]thiadiazole    92
6.2 Synthesis of 4,7-dibromo-5-fluorobenzo[c][1,2,5]thiadiazole    93
6.3 Synthesis of 5-fluorobenzo[c][1,2,5]thiadiazole    93
6.4 Synthesis of 4,7-dibromo-5,6-difluorobenzo[c][1,2,5]thiadiazole    94
6.5 Synthesis of 4,7-bis(4-(1,2,2-triphenylvinyl)phenyl) benzo[c][1,2,5]thiadiazole    94
6.6 Synthesis of 5-fluoro-4,7-bis(4-(1,2,2-triphenylvinyl)phenyl)benzo[c][1,2,5]thiadiazole    95
6.7 Synthesis of 5,6-difluoro-4,7-bis(4-(1,2,2-triphenylvinyl)phenyl)benzo[c][1,2,5]thiadiazole    96
Appendix.    97


                                

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全文公開日期 2023/01/26 (校內網路)
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