二茂鐵輪烷晶體之光照引發機械運動｜國立清華大學博碩士論文庫

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研究生：	陳宥廷 Chen, You-Ting
論文名稱：	二茂鐵輪烷晶體之光照引發機械運動 Photo-responsive mechanical motions of ferrocene-based anthryl rotaxane crystals
指導教授：	堀江正樹 Horie, Masaki
口試委員:	王潔 Wang, Jane 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：	2018
畢業學年度：	106
語文別：	英文
論文頁數：	78
中文關鍵詞：	超分子化學、晶體分子機械
相關次數：	點閱：3 下載：0
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　　本篇論文將探討具有光反應性之輪烷超分子，此輪烷超分子之軸分子含二茂鐵及蒽結構，並與冠醚環分子所共同組成。藉由在二茂鐵軸分子中導入蒽作為取代基，該輪烷超分子晶體將同時擁有兩者的光引發機械運動，可應用發展為具獨特光引發效應之晶體分子機械，因此將針對該含蒽二茂鐵輪烷超分子之溶液與晶體特性進行測量及探討。
　　在第二章前半部分當中，主要著重於含蒽二茂鐵輪烷超分子的合成，藉由測量核磁共振氫譜、質譜分析確認該分子；並透過分析其單晶之X射線晶體學得知其分子結構。第二章後半部分詳述該輪烷超分子於溶液狀態與晶體狀態下之性質探討，首先溶液態透過紫外¬－可見分光光度法量測吸收光譜，得知蒽吸收介於300至400奈米波長光，二茂鐵則吸收450奈米波長光；透過螢光光譜量測發射光譜確認蒽之螢光特性。此外也發現溶液態下照射紫外雷射光會導致蒽發生氧化反應，該氧化反應被預期可作為新發現之輪烷分子封端反應。於第二章最後探討含蒽二茂鐵輪烷超分子晶體之光引發機械運動，其晶體可藉由雷射光照射產生顯著的體積變化。
　　第三章將對該研究計畫所得成果進行結論，此外也提出未來可延伸進行之研究主題方向；第四章當中詳細總結並整理本項研究中所使用之方法、儀器與測量結果。

　　In this thesis, photo-responsive [2]pseudorotaxanes composed of ferrocene and anthryl groups in an axle and crown ether ring are reported. Here, we introduce anthracene group in ferrocene-containing [2]pseudorotaxane and attempt photochemical reaction in crystal and solution state. The photo-induced mechanical motions are unique and important for development of crystalline molecular machines.
　　In Chapter 2, the synthesis, characterization, and optical properties of the new [2]pseudorotaxane, [(Fc-anthryl)·DB24C8]+(PF6)-, are described. Obtained [2]pseudorotaxane was characterized by NMR and mass spectrometry. The molecular structure was confirmed by single-crystal X-ray crystallography. The optical properties of the pseudorotaxane were examined by UV-vis absorption and fluorescence emission spectroscopies in solution. The results revealed that the pseudorotaxane absorbed light in a range between 300 nm and 400 nm owing to anthryl group and around 450 nm because of ferrocenyl group. In addition, we discovered the oxidation of anthryl group to provide anthraquinone group induced by UV irradiation. This can be applied to end-capping reaction to convert the pseudorotaxane into rotaxane. Finally, the photo-responsive mechanical motions of the crystals are described. Crystals of [2]pseudorotaxane show significant volume change induced by photoirradiation.
　　In Chapter 3, conclusions and future works are described. Experimental details are summarized in Chapter 4.

Abstract    I
中文摘要    II
Table of Contents    III
Chapter 1　　Introduction and aim    1
1　　Supramolecular chemistry    1
2　　Mechanically-interlocked molecular architectures    2
3　　Applications of supramolecular chemistry    4
3.1　　Molecular machines    4
3.2　　Molecular switches    8
3.3　　Crystalline Molecular Machines    9
3.4　　Rapid and reversible photoinduced switching of a rotaxane crystal    11
3.5　　Photoinduced photochemical reactions driven mechanical motion of anthracene crystals    15
4　　Aim of the work    20
Chapter 2　　Synthesis and characterization of crown ether ferrocene-based anthryl rotaxane    24
1　　Introduction    24
2　　Synthesis of ferrocene-containing pseudorotaxane    25
2.1　　Preperation of Ferrocenemethylamine    25
2.2　　Preperation of 2-(bromomethyl)anthracene    26
2.3　　Preperation of [(Fc-anthryl)·DB24C8]+(PF6)-    27
3　　Characterization of [(Fc-anthryl)·DB24C8]+(PF6)-    29
3.1　　NMR analysis    29
3.2　　Mass spectrometry analysis    34
3.3　　Single-crystal X-ray crystallography    37
4　　Optical properties of [(Fc-anthryl)·DB24C8]+(PF6)- in solution.    39
4.1　　Photochemical reaction in solution    39
4.2　　UV-vis absorption spectra    40
4.3　　Fluorescence emission spectra    43
4.4　　Mass spectrometry analysis of irradiated solution    47
5　　Properties of [(Fc-anthryl)·DB24C8]+(PF6)- crystal    49
5.1　　Thermal properties    49
5.2　　Optical properties    50
6　　Photo-responsive mechanical motion of crystals    52
Chapter 3　　Conclusion and future works    57
1　　Conclusion    57
2　　Future works    59
Chapter 4　　Experimental section    61
1　　General methods    61
2　　Experimental method    62
2.1　　Photo-induced size change measurement    62
2.2　　Measurement of the time dependence of the displacement    62
2.3　　Birefringence measurement    63
2.4　　Single crystal X-ray crystallography    63
3　　Preparation of ferrocenecarbaldehyde oxime    64
4　　Preparation of ferrocenemethylamine (FCMA)    65
5　　Preparation of 2-Methylanthracene    66
6　　Preparation of 2-(Bromomethyl)anthracene    68
7　　Preparation of [(Fc-anthryl)]+PF6-    69
8　　Preparation of [(Fc-anthryl)·DB24C8]+(PF6)-    71
9　　X-ray single crystallography    73
References    75


                                

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