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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 楊吉水(Jye-Shane Yang) | |
| dc.contributor.author | I-Tsun Lee | en |
| dc.contributor.author | 李依純 | zh_TW |
| dc.date.accessioned | 2021-06-16T23:55:44Z | - |
| dc.date.available | 2017-07-20 | |
| dc.date.copyright | 2012-07-20 | |
| dc.date.issued | 2012 | |
| dc.date.submitted | 2012-07-18 | |
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/65642 | - |
| dc.description.abstract | 本論文主要是合成與探討分子煞車系統IMe 與IAn，以五苯荑為轉子，吲哚
衍生物為分子煞車器，煞車器與轉子間以可進行順反式異構化之雙鍵連結，以期 應用於光電控制之分子機械元件設計。利用變溫1H 和13C NMR 圖譜、DFT 理論 計算，探討轉子於煞車前與煞車後之轉動動能與動力學參數。當化合物於順式結 構時（cis-IMe ，cis-IAn），煞車器與轉子間由於立體障礙因素，使轉子之單鍵 旋轉速率較慢（煞車開啓），而當化合物於反式結構時（trans-IMe，trans-IAn） 煞車器與轉子間則因無明顯立體障礙，使轉子有較快的旋轉速率（煞車關閉）， 轉子於煞車開啓與關閉狀態間旋轉速率差可達108 倍。 此分子煞車系統之控制，則是利用煞車器與轉子間連接之雙鍵，在二氯甲烷 溶劑中之順反異構化進行煞車轉換。以反式化合物（trans-IMe，trans-IAn）為起 始物，利用大於370 奈米波長為激發光源，當達到光反應穩定狀態時，反式異構 物轉換為順式異構物之效率可達90％以上，此乃由於化合物於反式結構時於370 奈米波長之吸收度較大，因此可有效率被激發至激發態，進而進行異構化反應。 同樣，順式異構物可經由激發290 奈米波長，轉換回反式異構物，當達到光反應 穩定狀態時，兩者比例約為55:45 （順式：反式），由於吸收光譜之重疊性，使 得順式異構物利用光為能源時，轉換為反式異構物之效率較差。另一方面，若使 用電化學氧化方式，將順式異構物經由陽離子自由基中間體，轉換為反式異構物 之單次轉換效率則可達72%，但由於化合物對於電化學實驗之低穩定性， 使其無 法成為一理想光電轉換之分子煞車系統。 | zh_TW |
| dc.description.abstract | We designed pentiptycene-indole-derived molecular brakes IMe and IAn for the
purpose of achieving both high switching efficiency and efficient brake performance. Rotational rate and kinetic parameters were deduced form variable-temperature 1H and 13C NMR simulation and DFT calculation. The rotational rate could reach 108 -folded difference between brake on and brake off states. We compared 2 different energy input, light and electric energy, for isomerization switch of the compounds. For photoisomerization switch, the efficiency could reach > 90% from trans isomers to corresponding cis isomers when the compound was irradiated with > 370 nm light. The high switching efficiency was because of the larger absorbance for trans isomers at the wavelength. However, the photoisomerization switching efficiency was only 45% for cis isomers to corresponding trans isomers for their overlapping absorption spectra. On the other hand, the electrochemical isomerization switch could reach 72% efficiency from cis-IMe to thermodynamically stable trans-IMe through a cation radical intermediate. However, because of the instability of indole moiety upon electric pulse, the pentiptycene-indole-derived molecular brakes are not ideal systems with electric energy input. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-16T23:55:44Z (GMT). No. of bitstreams: 1 ntu-101-R99223126-1.pdf: 29028811 bytes, checksum: 24b371bff06e72ce7fcb311883a2984f (MD5) Previous issue date: 2012 | en |
| dc.description.tableofcontents | 謝誌 .......................................................................................................................................... I
摘要 ........................................................................................................................................ II Abstract ................................................................................................................................. III Table of Contents .................................................................................................................. IV List of Figures ........................................................................................................................ VI List of Tables ........................................................................................................................... X List of appendix ..................................................................................................................... XI Chapter 1 Introduction ............................................................................................................ 1 1-1 Molecular machine ........................................................................................................ 1 1-1-1 Characteristics of molecular machines ..................................................................... 1 1-1-2 Examples of molecular machine with linear movement ........................................... 3 1-1-3 Examples of molecular machine with rotary motion ................................................ 7 1-1-4 Examples of molecular machine with other motions .............................................. 10 1-2 Isomerization of alkene ................................................................................................ 11 1-2-1 Photoisomerization of alkene .................................................................................. 11 1-2-2 Chemicals-catalyzed isomerization of alkene ......................................................... 12 1-2-3 Electron-catalyzed isomerization of alkene ............................................................ 13 1-3 Iptycene .......................................................................................................................... 14 1-3-1 Structure and nomenclature of iptycene .................................................................. 14 1-3-2 Pentiptycene ............................................................................................................ 15 1-3-3 Functionalization of pentiptycene ........................................................................... 15 1-3-4 Molecular rotors with pentiptycene ......................................................................... 17 1-4 Electrochemistry of indoles .......................................................................................... 21 1-5 Motivation ..................................................................................................................... 23 Chapter 2 Results and discussion ......................................................................................... 24 2-1 Synthesis ........................................................................................................................ 24 2-1-1 The target compounds and retrosynthesis ............................................................... 24 2-1-2 Synthesis of target compounds ................................................................................ 25 2-2 The Structure and characterization ............................................................................ 29 2-2-1 Theoretical calculation for IMe ............................................................................... 29 2-2-2 Structure of cis-IMe, cis-IAn and NMR spectra ..................................................... 32 2-2-3 The variable-temperature NMR spectra and 13C-NMR spectra simulation of cis- IMe and cis-IAn ................................................................................................................ 35 2-3 Photoisomerization properties ..................................................................................... 41 2-3-1 UV-Vis. absorption spectra of IMe and IAn ........................................................... 41 2-3-2 Photoisomerization switch of IMe and IAn ............................................................ 42 2-4 Electrochemical Properties .......................................................................................... 44 2-4-1 CV and DPV spectra of IMe and IAn ..................................................................... 44 2-4-2 Electrochemical isomerization switch of IMe and IAn ........................................... 50 Chapter 3 Conclusion ............................................................................................................ 56 Chapter 4 Experimental section ........................................................................................... 57 4-1 Materials ........................................................................................................................ 57 4-2 Methods and Instruments ............................................................................................ 59 4-3 Synthesis and Structural characterization data ........................................................ 65 | |
| dc.language.iso | en | |
| dc.title | 以五苯荑-吲哚衍生物為主體之分子煞車合成與性質研究 | zh_TW |
| dc.title | Synthesis and Characterization of Pentiptycene-Indole-Derived Molecular Brakes | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 100-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 林英智(Ying-Chih Lin),鄭原忠(Yuan-Chung Cheng) | |
| dc.subject.keyword | 五苯荑,分子機械,分子煞車,吲,哚,核磁共振, | zh_TW |
| dc.subject.keyword | pentiptycene,molecular machine,molecular brake,indole,NMR simulation, | en |
| dc.relation.page | 129 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2012-07-18 | |
| 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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