偶氮苯超分子材料之光熱機械運動｜國立清華大學博碩士論文庫

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研究生：	林儀嘉 Lin, Yi-Chia
論文名稱：	偶氮苯超分子材料之光熱機械運動 Mechanical motions of azobenzene-containing supramolecular materials
指導教授：	堀江正樹 Horie, Masaki
口試委員:	周鶴修 Chou, Ho-Hsiu 游進陽 Yu, Chin-Yang
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2019
畢業學年度：	107
語文別：	英文
論文頁數：	134
中文關鍵詞：	準輪烷、單晶、順反異構化、光致機械運動、偶氮苯
外文關鍵詞：	pseudorotaxane, azobenzene, cis-trans isomerization, single crystal, photomechanical conversion
相關次數：	點閱：1 下載：0
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在此篇研究中，我們設計與合成了數種含有偶氮苯結構的分子機械，並以此類設計去探索嶄新的晶體中的分子動態反應。在此含有軸-環結構之分子機械中，選擇了含偶氮苯的銨鹽做為軸分子設計，並佐以不同官能基，例如：氫原子、甲氧基、甲苯基以了解不同官能基對分子機械的影響，而環分子則選擇環冠醚，例如：二苯並-18-冠-6醚或二苯並-24-冠-8醚等。分子機械晶體的結晶是由乙醚溶劑擴散至溶解度佳的溶液中形成的。所有的分子機械晶體均檢測過核磁共振光譜的氫譜、質譜儀和X-射線單晶繞射儀。研究中所有含偶氮苯分子機械的單晶均在445奈米或360奈米波長的雷射中進行光機械轉換的實驗，並有部分單晶可顯示可受特定雷射控制巨觀的分子型變。此篇研究也透過單晶中的分子排列進行分子機械晶體的光致運動變化的研究。這些可受光熱等外部刺激控制的晶體運動將可做為日後奈米尺度的元件設計。

In this research, we have designed and synthesized complexes comprising of azobenzene with various functional groups to explore new molecular dynamics in crystal state. Axle molecules with azobenzene-containing ammonium salt tethered with -H, -methoxyl, or -tolyl groups were complexed with dibenzo[18]crown-6 ether (DB18C6) or dibenzo [24]crown-8 ether (DB24C8) ring molecule in a soluble solution and they were crystalized by the ether vapor diffusion method. These complexes and axle molecule precursors were characterized by 1H NMR and mass spectrometry. Their molecular structures were also confirmed by single-crystal X-ray crystallography. Single crystals of these azobenzene-containing complexes were used for photomechanical conversion under alternating 360-nm and 445-nm laser irradiation, showing specific bending motions. These crystal dynamics were discussed based on their molecular structures obtained by single-crystal X-ray crystallography. The mechanical characteristics of such molecular machines could be applied to nano-microscale devices.

Abstract    II
摘要    III
Chapter 1　　Introduction and Aim    4
1.1　Supramolecular chemistry    4
1.1.1　History of supramolecular chemistry    4
1.1.2　Molecular machines and MIMs    6
1.1.3　Supramolecules in crystalline states    9
1.2　Functionalized crystals    10
1.2.1　Photo-induced properties of crystals    10
1.2.3　Other functionalized properties of crystals    18
1.3　Mechanism of azobenzene crystals and methodologies of conformation measurements    20
1.4　Aim of the work    27
Chapter2　　Synthesis and crystallization methodologies and characterization    31
2.1　Introduction: blueprint of completed experiments    31
2.2　Synthesis methodologies and characterization    33
2.3　Optimizations of synthesis    44
2.4　Crystallization    45
Chapter 3　　Photo- and thermally induced mechanical motions of azobenzene-containing complexes    48
3.1　Measurement methodologies    48
3.2　Appearances of crystals    51
3.3　Molecular alignment in a unit cell    52
3.3.1 Complex 1    52
3.3.2 Series of Complex 2    56
3.4　Photo-induced properties    62
3.4.1 Complex 1a    62
3.4.2 Complex 1b    63
3.4.3 Series of Complex 2    65
3.5　Thermal-induced properties    67
3.5.1 Complex 1a    67
3.5.2 Complex 1b    67
3.5.3 Series of Complex 2    68
Chapter 4　　Photo- and thermal-induced mechanical motions of Complex 3 series    71
4.1　Appearance of crystals    71
4.2　Molecular alignment in a unit cell    71
4.3　Characterizations of crystals    77
4.4　Discussion and summary of this chapter    80
Chapter 5　　Discussions    81
Chapter 6　　Summary and future prospective    95
Appendix　　Experimental section    96
A.1　 General synthesis methods    96
A.2　Preparation of precursors    97
Synthesis of 4-((4-methoxyphenyl)diazenyl)benzonitrile:    97
Synthesis of (4-((4-methoxyphenyl)diazenyl)phenyl)methanamine:    98
Synthesis of 1,1’-Ferrocenedicarboxaldehyde:    99
A.3　Preparation of Complex 1    102
Synthesis of (E)-(4-((4-methoxyphenyl)diazenyl)phenyl)methanaminium chloride:    102
Synthesis of Axle 1    102
Synthesis of Complex 1    103
A.4　Preparation of Complex 2    107
Synthesis of (E)-N-(4-((E)-(4-methoxyphenyl)diazenyl)benzyl)-1-(p-tolyl)methanimine:    107
Synthesis of (E)-N-(4-((4-methoxyphenyl)diazenyl)benzyl)-1-(p-tolyl)methanamine:    107
Synthesis of (E)-N-(4-((4-methoxyphenyl)diazenyl)benzyl)-1-(p-tolyl)methanaminium chloride:    108
Synthesis of Complex 2    110
A.5　Preparation of Complex 3    116
Synthesis of 1,1’-ferrocenyldimethylimine-4-(4’- methoxyl)diazenyl)phenyl)methanamine    116
Synthesis of Axle 3    117
Synthesis of Complex 3    118
A.6　X-ray single crystallography    123
Precursor    123
Axle 2    124
Complex 1a    125
Complex 1b    126
Complex 2    127
Complex 3    128
References    132

                                

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