Synthesis and Characterization of Photo-responsive Rotaxanes with Biferrocenyl-containing Axle

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研究生：	陳安倩 Tan, Ann Chen
論文名稱：	Synthesis and Characterization of Photo-responsive Rotaxanes with Biferrocenyl-containing Axle 合成與分析：含雙二茂鐵之光反應超分子Rotaxane
指導教授：	堀江正樹 Horie, Masaki
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：	2016
畢業學年度：	104
語文別：	英文
中文關鍵詞：	超分子、單晶繞射、再結晶
外文關鍵詞：	supermolecule, biferrocene
相關次數：	點閱：1 下載：0
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A series of new [2]pseudorotaxanes “[2FcDB24C8](PF6) and [2FcDB24C8](PF6) (X = Br or I)”, composed of dibenzo[24]crown-8 ether (DB24C8) or tetrahalide substituted DB24C8 (DB24C8-X4) as a ring molecule have been synthesized. Being more comprehensible, these pseudorotaxanes are named 1, 2 and 3. The synthesis of biferrocene-containing axle molecule was carried out by the following steps. Ferroceneboronic acid served as a starting material. This was converted to iodoferrocene by addition of N-iodosuccinimide followed by Ullmann coupling to produce biferrocene. In between, different reaction conditions were attempted. Hence, optimization of reaction is reported in Chapter 2.3. The resulting products were identified by 1H NMR spectroscopy (500 MHz, CDCl3, r.t.) in every step. In the analysis section, we examined the response of the new [2FcDB24C8](PF6) crystals to laser irradiation at 445 nm, which intensity was comparable to the previously reported crystals of mono-ferrocene-containing [2]pseudorotaxane, [FcDB24C8](PF6) or pseudorotaxane 4. We have foreseen a rapid and reversible deformation of the crystals, as observed under optical microscope. From the X-ray single crystallography, we then studied the molecular interaction within the crystal and justified that it was due to the intra- and the intermolecular - interactions. Optical anisotropy, in particular thermal phase transition of the single crystals of the pseudorotaxane, was analyzed by polarizing optical microscopy (POM) with a Berek compensator. Furthermore, phase transition of the three types of crystals in respond to thermal stimuli was observed from POM images, differential scanning calorimetry (DSC), and X-ray crystallography.

Acknowledgement    I
Abstract    II
Table of Contents    III
List of Figures    V
List of Tables    X
Chapter 1    Introduction and Aim    11
1.1    Introduction to Supramolecular Chemistry    11
1.2    Supramolecular Chemistry: Interlocked Molecular Architectures    14
1.3    Application of Supramolecular Chemistry    18
1.4    Solid-state Crystalline Machines at Molecular Level    29
1.5    Molecular Motion of Single Crystals Induced by Stimuli    32
1.6    Aim of Work    38
Chapter 2    Synthesis of Pseudorotaxanes Composed of Crown Ether Ring & Biferrocenyl Axle Molecule    40
2.1    Introduction to Ferrocenyl Pseudorotaxane    40
2.2    Schematic of Pseudorotaxane Synthesis    44
2.3    Optimization of Synthesis Reactions    49
2.3.1    Optimization of Biferrocene Synthesis    49
2.3.2    Optimization of Biferrocene-carboxaldehyde Synthesis    52
Chapter 3    Characterization and Analysis of Photo-responsive Pseudorotaxane Single Crystals Composing Biferrocenyl-containing Axle with Different Crown Ether Rings    57
3.1    Introduction    57
3.2    X-ray Crystallography of Crystals    59
3.2.1    Analogy of crystallographic data among crystals    59
3.2.2    Miller indices of crystals    62
3.2.3    Intra-molecular and inter molecular interaction of crystals    65
3.3    Thermal Analysis of Biferrocenyl-axle Pseudorotaxanes    69
3.4    Photo-responsive Pseudorotaxane Crystals    75
Chapter 4    Conclusion and Future Work    79
Chapter 5    Experimental Section    80
5.1    General Methods    80
5.2    Optical Measurement for Laser Irradiation and Thermal Phase Transition    81
5.3    Preparation of Iodoferrocene    83
5.4    Preparation of Biferrocene    84
5.5    Preparation of Biferrocene-carboxaldehyde    85
5.6    Preparation of p-xylyl(biferrocenylmethyl)ammonium hexafluorophosphate, [2Fc-H]+(PF6)-    88
5.7    Preparation of [2]pseudorotaxane: [2Fc·DB24C8](PF6), [2Fc·DB24C8-Br4](PF6) & [2Fc·DB24C8- I4](PF6)    91
Appendix    95
Crystallographic data of [2FcDB24C8](PF6)    95
Crystallographic data of [2FcDB24C8](PF6) after heated to phase transition    104
Crystallographic data of [2FcDB24C8-Br4](PF6)    111
References    120

                                

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