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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 楊吉水(Jye-Shane Yang) | |
| dc.contributor.author | Fen-Miao Hou | en |
| dc.contributor.author | 侯玢妙 | zh_TW |
| dc.date.accessioned | 2021-06-16T02:51:07Z | - |
| dc.date.available | 2020-07-20 | |
| dc.date.copyright | 2015-07-20 | |
| dc.date.issued | 2015 | |
| dc.date.submitted | 2015-07-14 | |
| dc.identifier.citation | 1. Balzani, V.; Credi, A.; Raymo, F. M.; Stoddart, J. F., Artificial molecular machines. Angew. Chem. Int. Ed. 2000, 39 (19), 3348-3391.
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/54335 | - |
| dc.description.abstract | 五苯荑分子具有三度空間、結構剛硬且具有高對稱性的性質，此外，結構中具有U-及V-形凹槽，所以插入〝栓子〞時就可以達到分子煞車的效果。本篇論文主要合成並探討有別於以往實驗室以單軸為設計概念的分子煞車系統，以五苯荑分子作為轉子(rotor)；stiff-stilbene 兼具定子(stator) 及煞車器(brake-unit) 兩角色，設計出雙軸分子煞車系統化合物3。
我們利用氫譜與碳譜VT-NMR來探討五苯荑分子於室溫轉動快慢，並利用譜線形狀分析(LSA) 得到順式組態轉動的動力學參數。(Z)-3 中轉子與煞車器之間由於立體障礙造成旋轉速度減緩，達到煞車啟動(brake-on)；(E)-3 的X-ray單晶顯示轉子與煞車器之間不具有立體障礙，所以轉子可以自由旋轉，為煞車關閉(brake-off) 的狀態。另外，化合物3 於正己烷溶劑中的光化學控制達轉換效率為26 %，具有可逆性及重複性。化合物 3 除了具分子煞車的功能外，分子也具有聚集誘導放光(AIE) 效應。我們利用(E)-3 及 (Z)-3 來證實五苯荑分子旋轉的快慢將會影響其放光程度，亦即我們所設計的分子煞車系統的放光具有自由旋轉子效應(free rotor effect)。 | zh_TW |
| dc.description.abstract | Molecular brake is a type of molecular devices that could reversibly slow down the motions of a molecular subunit through external stimuli. We have reported a series of
light- and electrochemically driven molecular brakes using a rigid and H-shaped pentiptycene group as a four-bladed rotor. In this thesis, we designed molecule 3, which consists of a pentiptycene rotor, an indane brake-unit, and an indane stator, as a new generation of light-gated molecular brake. Experimental results show that rotation of the pentiptycene rotor is fast in (E)-3 but slow in (Z)-3 at 298 K. Furthermore, compound 3 can be reversibly and repetitive switched by light with a net efficiency of 26 % in n-hexane. In addition, compound 3 has the properties of aggregation-induced emission (AIE-effect). A combination of the luminescence and brake properties allows one to prove the concept of free rotor effect on photoluminescence, which cannot be achieved with our previous molecular brake systems. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-16T02:51:07Z (GMT). No. of bitstreams: 1 ntu-104-R02223147-1.pdf: 20738956 bytes, checksum: 899f30ffb64aec2f1229e2890a83f0cc (MD5) Previous issue date: 2015 | en |
| dc.description.tableofcontents | 謝誌 ii
中文摘要 v Abstract vi 目錄 vii 圖目錄 xi 表目錄 xvii 附圖目錄 xviii 第一章 前言 1 1-1 分子機械 (Molecular machines)1 1 1-2 人造分子機械 3 1-2-1 人造分子機械之要素 3 1-2-2 人造分子機械的分類 4 1-2-2.1分子馬達 (molecular motor) 6 1-2-2.1.1布朗運動 (Brownian motion) 6 1-2-2.1.2非布朗運動 (non-Brownian motion) 6 1-2-2.2分子開關 (molecular switch) 9 1-2-2.2.1分子開關-旋轉運動 9 1-2-2.2.2分子開關-線性運動 12 1-3 光學異構化作用 (photoisomerization) 13 1-3-1 單向異構化過程 (process of one-way isomerization)15a,15b 16 1-3-2 雙鍵異構化機制 21 1-3-2.1 OBF (one-bond flip mechanism)23 21 1-3-2.2 HT (hula-twist mechanism) 21 1-3-2.3 BP (bicycle-pedal mechanism)24 23 1-3-3 二苯乙烯光異構化25 25 1-3-4 Stiff-stilbene光異構化27 26 1-4 Stiff-stilbene的特徵 (characteristics of stiff-stilbene)29 29 1-4-1 分子結構 (molecular structure) 29 1-4-2 分子異構化之特性 31 1-4-3 應用 (application)32 35 1-5 聚集誘導發光 (aggregation-induced emission, AIE)33 37 1-6動力學NMR (Dynamic NMR, DNMR)38 41 1-6-1 譜線形狀分析 (line-shape analysis, LSA) 42 1-6-2 交換訊號光譜圖 (2D-exchange spectroscopy, 2D-EXSY) 44 1-7 苯荑 (iptycene) 分子介紹 47 1-7-1 苯荑分子的結構與命名 47 1-7-2 五苯荑分子 48 1-7-3 五苯荑分子之官能基化 48 1-7-4 五苯荑分子的應用44 51 1-7-4.1 作為化學感應分子40d 51 1-7-4.2 應用在有機硫醇的金屬表面45 52 1-7-4.3 五苯荑分子之分子機械 53 1-8 研究動機 59 第二章 結果與討論 61 2-1 化合物之合成 61 2-1-1 目標化合物之逆合成分析 61 2-1-2 目標分析物之合成 63 2-1-3 目標分析物的瓶頸 70 2-2 化合物的結構與特性 70 2-2-1 化合物(E)-3 之NMR圖譜結構鑑定與標定 71 2-2-2 VT-NMR 預測化合物(E)-3 之旋轉運動 76 2-2-3 化合物(E)-3 之X-ray單晶繞射結構 79 2-2-4 化合物(Z)-3 之NMR圖譜結構鑑定與標定 80 2-2-5 VT-NMR 測量化合物(Z)-3 之旋轉運動 84 2-3 化合物 3 的光學性質 91 2-3-1 化合物 3 之吸收光譜圖 91 2-3-2 化合物 3 之光異構化性質 92 2-3-3 化合物 3 之整體轉換 96 2-4 化合物 3 之AIE 效應 98 2-4-1 化合物3之放光光譜圖 98 2-4-2 AIE實驗結果與討論 102 2- 5 化合物 3 之自由旋轉子效應 (free rotor effect) 105 2-5-1自由旋轉子效應 (free rotor effect) 105 2-5-2設計概念 109 2-5-3 證明自由旋轉效應之操作環境及樣品配置 110 2-5-4 自由旋轉效應之實驗結果與討論 111 第三章 結論 117 第四章 實驗部分 118 4-1 實驗藥品與溶劑 118 表4- 1 實驗所使用之藥品 118 4-2 實驗儀器及設定與操作 122 4-3 實驗黏滯度參數 65 128 4-4實驗步驟 129 4-4-1旋轉子─五苯荑分子的合成 129 4-4-2化合物1及2之煞車器 (brake-unit) ─ 金鋼烷分子的合成 131 4-4-3化合物1合成 132 4-4-4化合物2合成 137 4-4-5化合物3合成 140 文獻資料 145 附圖 155 | |
| dc.language.iso | zh-TW | |
| dc.title | 五苯荑衍生之新型光控分子煞車系統 | zh_TW |
| dc.title | A New Generation of Pentiptycene-Derived Light-Gated Molecular Brakes | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 103-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 林英智(Ying-Chih Lin),鄭原忠(Yuan-Chung Cheng),趙奕姼(Ito Chao) | |
| dc.subject.keyword | 分子煞車,五苯荑,自由旋轉子效應, | zh_TW |
| dc.subject.keyword | molecular brake,pentiptycene,free-rotor effect, | en |
| dc.relation.page | 206 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2015-07-14 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| 顯示於系所單位： | 化學系 | |
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