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研究生:吳恬迪
研究生(外文):Wu, Tiend-Di
論文名稱:Synthesis and optical properties of pseudorotaxane crystals
指導教授:堀江正樹
指導教授(外文):Masaki Horie
學位類別:碩士
校院名稱:國立清華大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:英文
論文頁數:134
中文關鍵詞:超分子化學分子機器
外文關鍵詞:Supramolecular chemistryMolecular machinePseudorotaxnaeCrystal optical materials
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In this thesis, molecular alignment of pseudorotaxanes in single crystal state and an optical anisotropy of the crystals are described.
In Chapter 2, a series of new pseudorotaxanes having interlocked structure of dibenzo[24]crown-8 ether (DB24C8) or 4,4’,5,5’-tetrabromodibenzo[24]crown-8 ether (DB24C8-Br4) and axle molecules based on ammonium cation are synthesized changing substituents of tolyl and phenyl groups in the axle molecules. Pseudorotaxane structures are analyzed by X-ray single crystallography, which shows that the pseudorotaxanes are stabilized their supermolecular structures by following non-covalent interactions in solid state: (1) hydrogen bonds (N+-H…O and C-H…O) between the oxygen acceptor atoms of the DB24C8 or DB24C8-Br4 ring molecule and the hydrogen donor atoms of the cation’s NH2+ and CH2 groups, (2) pi-pi intramolecular interactions between aromatic part of ring molecules and tolyl or phenyl part of axle molecules, and (3) pi-pi intermolecular interactions between aromatic rings. These crystallographic data are used for discussion of optical properties of pseudorotaxane crystals. The crystals of pseudorotaxanes having pi-pi intramolecular interactions tend to show higher birefringence value. On the other hand, the pseudorotaxanes with C-H…pi intramolecular interactions instead of the pi-pi intramolecular interactions give lower birefringence value.
Chapter 3 shows that [2]pseudorotaxanes composed of ferrocene-containing axle with DB24C8 act as a thermally-driven molecular switch in the single-crystal state. The pseudorotaxane structure can be altered reversibly in the single crystal state by thermal stimulation by observation of differential scanning calorimetry (DSC) and polarized optical microscope combined with hot stage. When the counter anion is replaced from PF6− to AsF6−, the pseudorotaxane molecule applies C-H…pi intramolecular interaction which does not show crystal-to-crystal phase-transition. Birefringence values of these crystals are measured changing composition ratios of the counter anions (PF6−/AsF6−). The pseudorotaxanes with higher PF6− compositions show higher birefringences due to well-aligned aromatic rings derived from pi-pi interactions, whereas those with higher AsF6− compositions exhibit lower birefringence because of less ordered C-H…pi interactions.

Abstract I
Table of Contents III
Chapter 1. Introduction and aim 1
1.1 Introduction of supramolecular chemistry 1
1.2 Molecular machines 7
1.3 Movements of molecules in solid state 16
1.4 Applications of switchable rotaxane 19
1.5 Movements of Pseudorotaxanes in crystal state 22
1.6 Aim of the work 24
Chapter 2. Synthesis and optical properties of pseudorotaxanes composed of crown ether and ammonium cation 25
2.1 Introduction 25
2.2 Synthesis of pseudorotaxanes 27
2.3 X-ray single crystallography 36
2.4 Thermal properties 50
2.5 Optical properties 57
2.6 Conclusion 60
Chapter 3. Optical properties of pseudorotaxanes composed of crown ether with ferrocene-containing axis molecule 61
3.1 Introduction 61
3.2 Optical properties 65
3.3 Conclusion 79
Chapter 4. Experimental section 80
4.1 General methods 80
4.2 Preparation of bis(4-methylbezyl)ammonium hexafluorophosphate, [1H]+(PF6)- 85
4.3 Preparation of 4-methylbenzyl ammonium hexafluorophosphate, [2H]+(PF6)- 88
4.4 Preparation of dibenzylammonium hexafluorophosphate, [3H]+(PF6)- 90
4.5 Preparation of (benzyl)(2-phenylethyl)ammonium hexafluorophosphate, [4H]+(PF6)- 92
4.6 Preparation of (2-phenylethylamine)(4-methylbezyl)ammonium hexafluorophosphate, [5H]+(PF6)- 94
4.7 Preparation of (2-p-tolylethylamine)(benzyl)ammonium hexafluorophosphate, [6H]+(PF6)- 96
4.8 Preparation of (2-p-tolylethylamine)(4-methylbezyl)ammonium hexafluorophosphate, [7H]+(PF6)- 98
4.9 Preparation of (1-Adamantane-methyl)(4-methylbezyl)ammonium hexafluorophosphate, [8H]+(PF6)- 100
4.10 Preparation of 4,4’,5,5’-tetrabromodibenzo[24]crown-8 ether 102
4.11 Preparation of [2]pseudorotaxanes: [1DB24C8-Br4](PF6), [2DB24C8-Br4](PF6) and [3DB24C8-Br4](PF6) 104
4.12 Preparation of [2]pseudorotaxanes: [1DB24C8](PF6), [2DB24C8](PF6) and [3DB24C8](PF6) 109
4.13 Preparation of [2]pseudorotaxanes: [4DB24C8-Br4](PF6), [5DB24C8-Br4](PF6), [6DB24C8-Br4](PF6) and [7DB24C8-Br4](PF6) 111
4.14 Preparation of [2]pseudorotaxanes: [4DB24C8](PF6), [5DB24C8](PF6), [6DB24C8](PF6) and [7DB24C8](PF6) 117
4.15 Preparation of [2]pseudorotaxanes of [8DB24C8-Br4][PF6] and [8DB24C8][PF6] 122
4.16 X-ray single crystallography 125
Chapter 5. Conclusion 129
References 131


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