Synthesis and optical properties of pseudorotaxane crystals

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研究生：	吳恬迪 Wu, Tiend-Di
論文名稱：	Synthesis and optical properties of pseudorotaxane crystals
指導教授：	堀江正樹 Masaki Horie
口試委員:	蘇安仲 Su, An-chung 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：	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：	Molecular machine, Pseudorotaxnae, Crystal optical materials
相關次數：	點閱：3 下載：0
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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    Introduction of supramolecular chemistry    1
2    Molecular machines    7
3    Movements of molecules in solid state    16
4    Applications of switchable rotaxane    19
5    Movements of Pseudorotaxanes in crystal state    22
6    Aim of the work    24
Chapter 2.    Synthesis and optical properties of pseudorotaxanes composed of crown ether and ammonium cation    25
1    Introduction    25
2    Synthesis of pseudorotaxanes    27
3    X-ray single crystallography    36
4    Thermal properties    50
5    Optical properties    57
6    Conclusion    60
Chapter 3.    Optical properties of pseudorotaxanes composed of crown ether with ferrocene-containing axis molecule    61
1    Introduction    61
2    Optical properties    65
3    Conclusion    79
Chapter 4.    Experimental section    80
1    General methods    80
2    Preparation of bis(4-methylbezyl)ammonium hexafluorophosphate, [1H]+(PF6)-    85
3    Preparation of 4-methylbenzyl ammonium hexafluorophosphate, [2H]+(PF6)-    88
4    Preparation of dibenzylammonium hexafluorophosphate, [3H]+(PF6)-    90
5    Preparation of (benzyl)(2-phenylethyl)ammonium hexafluorophosphate, [4H]+(PF6)-    92
6    Preparation of (2-phenylethylamine)(4-methylbezyl)ammonium hexafluorophosphate, [5H]+(PF6)-    94
7    Preparation of (2-p-tolylethylamine)(benzyl)ammonium hexafluorophosphate, [6H]+(PF6)-    96
8    Preparation of (2-p-tolylethylamine)(4-methylbezyl)ammonium hexafluorophosphate, [7H]+(PF6)-    98
9    Preparation of (1-Adamantane-methyl)(4-methylbezyl)ammonium hexafluorophosphate, [8H]+(PF6)-    100
10    Preparation of 4,4’,5,5’-tetrabromodibenzo[24]crown-8 ether    102
11    Preparation of [2]pseudorotaxanes: [1DB24C8-Br4](PF6), [2DB24C8-Br4](PF6) and [3DB24C8-Br4](PF6)    104
12    Preparation of [2]pseudorotaxanes: [1DB24C8](PF6), [2DB24C8](PF6) and [3DB24C8](PF6)    109
13    Preparation of [2]pseudorotaxanes: [4DB24C8-Br4](PF6), [5DB24C8-Br4](PF6), [6DB24C8-Br4](PF6) and [7DB24C8-Br4](PF6)    111
14    Preparation of [2]pseudorotaxanes: [4DB24C8](PF6), [5DB24C8](PF6), [6DB24C8](PF6) and [7DB24C8](PF6)    117
15    Preparation of [2]pseudorotaxanes of [8DB24C8-Br4][PF6] and [8DB24C8][PF6]    122
16    X-ray single crystallography    125
Chapter 5.    Conclusion    129
References    131


                                

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