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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 楊吉水(Jye-Shane Yang) | |
dc.contributor.author | Pei-Wei Li | en |
dc.contributor.author | 李培瑋 | zh_TW |
dc.date.accessioned | 2021-06-17T01:36:09Z | - |
dc.date.available | 2025-07-31 | |
dc.date.copyright | 2020-09-14 | |
dc.date.issued | 2020 | |
dc.date.submitted | 2020-08-25 | |
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K., Inorganic chemistry: principles of structure and reactivity. Pearson Education India: 2006. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/67527 | - |
dc.description.abstract | 在我們實驗室過去的工作中,我們在含有間位 (meta-) 胺基的剛性二苯乙烯衍生物中觀察到了高強度的螢光,其螢光量子產率在正己烷中高達0.73,並且在順式結構中能保有非常強的螢光,是順式二苯乙烯系列分子非常罕見的。而在鄰位 (ortho-) 胺基取代之剛性二苯乙烯衍生物中,我們可以透過胺基上甲基的訊號來分析分子在基態下的螺旋反轉運動,亦是較少可以探討螺旋反轉運動的例子,而由於光異構化反應而使此化合物之螢光被焠熄。 在此工作中,我們將間位胺基引入於鄰位胺基取代剛性二苯乙烯之另一側苯環,設計出含鄰位-間位之omDASS分子,欲使其具有螢光的表現,並探討其在光物理性質與扭轉運動之間的關係,而我們同時合成了雙間位 (mmDASS) 之分子,探討雙胺基系統之光物理現象。在 (E)-mmDASS分子在正己烷中觀察到了較單間位胺基取代化合物來得弱的放光,僅有0.42的螢光量子產率,然而在高極性之乙腈中,則呈現相反的趨勢,擁有高達0.79的螢光量子產率,是由於該化合物中,溶劑效應在1t*及1p*兩能階所造成的效應不同所致。而對於化合物 (E)-omDASS,我們成功地使其有些微螢光表現,並在動力學NMR的實驗中,反式異構物的訊號變化可以用來分析基態下的剛性二苯乙烯之螺旋反轉運動,而順式異構物則可以看到胺基旋轉的運動。透過光異構化量子產率的測量,發現其光異構化無法有效地受到間位胺基的抑制,仍有0.49的異構化量子產率,其原因為鄰位胺基會造成分子有較為扭曲的結構,因此助長了光異構化的反應發生。 | zh_TW |
dc.description.abstract | In our recent work, we observed strong fluorescence quantum yield up to 0.73 in hexane for stiff-stilbene derivatives bearing meta-amino group. And its cis isomer also had high fluorescence quantum yields in both hexane and acetonitrile. To our best knowledge, it’s the first example of cis-stilbene series that exhibited strong fluorescence. Moreover, ortho-amino substituted stiff-stilbene analyzed helical inversion in the ground state. It is also a rare example of a single small molecule that analyzes helical inversion. Unfortunately, the fluorescence was quenched because of fast photoisomerization. In this work, we synthesized omDASS by introducing a meta-amino group on the other side of phenyl ring of ortho-amino substituted stiff-stilbene. We predicted that the meta-amino group could enhance the fluorescence intensity by lowering the photoisomerization quantum yield. Thus we could discuss the fluorescence behavior and torsional motion in this system. Moreover, we synthesized bis-amino derivatives bearing meta-meta (mm-) amino groups on opposite sites to discuss its photophysical properties. We observed that the fluorescence intensity was weaker than the mono m-amino substituted one in the non-polar solvent. The fluorescence quantum yield of (E)-mmDASS was only 0.42 in hexane. However, the fluorescence quantum yield is up to 0.79 in acetonitrile. As for (E)-omDASS, we can also analyze the ground state motions in VT-NMR experiments. The fluorescence of (E)-omDASS is successfully turned on although the performance is not very well as expected because the photoisomerization of (E)-omDASS could not be inhibited efficiently due to the twisted conformation. | en |
dc.description.provenance | Made available in DSpace on 2021-06-17T01:36:09Z (GMT). No. of bitstreams: 1 U0001-1508202016520900.pdf: 12096876 bytes, checksum: 21143ab3422d968bf1d149bb29edf2fe (MD5) Previous issue date: 2020 | en |
dc.description.tableofcontents | 謝誌 i 中文摘要 iii Abstract iv 目錄 v 圖目錄 ix 表目錄 xiii 附圖目錄 xv 附錄圖 xvi 第一章 緒論 1 1-1 光化學 (photochemistry) 1 1-1-1 光物理 (photophysics) 2 1-1-1.1 吸收 (absorption) 2 1-1-1.2 放光 (emission) 2 1-1-1.3 量子產率 (quantum yield) 3 1-1-1.4 生命期 (lifetime) 3 1-1-2 光異構化 (photoisomerization) 4 1-1-2.1 One Bond Flip (OBF) 4 1-1-2.2 Hula Twist (HT) 5 1-1-2.3 Bicycle-Pedal (BP) 7 1-2 分子的旋轉運動 7 1-2-1 基態下的旋轉運動 7 1-2-1.1 動力學核磁共振光譜 8 1-2-1.2 譜線形狀分析 (line-shape analysis,LSA) 9 1-2-2 激發態下的分子運動 11 1-2-2.1 自由旋轉子效應 (free-rotor effect) 11 1-2-2.2 分子內旋轉的限制 12 1-2-2.3 聚集誘導發光 (AIE) 12 1-2-2.4 應用 14 1-3 二苯乙烯之特性 19 1-3-1 二苯乙烯之光物理及光化學 19 1-3-1.1 反式二苯乙烯 19 1-3-1.2 順式二苯乙烯 20 1-3-2 二苯乙烯之胺基取代效應 21 1-3-2.1 單胺基取代之二苯乙烯 21 1-3-2.2 雙胺基取代之二苯乙烯 22 1-3-3 立體效應 24 1-3-4 剛性二苯乙烯 25 1-3-4.1 剛性二苯乙烯之光物理性質 26 1-3-4.2 剛性二苯乙烯的應用 28 1-4 螢光量子產率的提升 (quantum yield enhancement) 31 1-4.1 結構限制 (structure confinement) 31 1-4.2 環境限制 (environment confinement) 31 1-4.3 電子效應限制 (electronic confinement) 32 1-5 研究動機 34 第二章 結果與討論 35 2-1 目標化合物之合成 35 2-1.1 Barton-Kellogg及McMurry反應合成雙鍵機制 35 2-1.2 目標化合物之合成 36 2-2 目標化合物之結構 41 2-2.1 (E)-mmDASS之X-ray晶體結構 41 2-2.2 (Z)-mmDASS之X-ray晶體結構 42 2-2.3 (E)-omDASS之X-ray晶體結構 43 2-2.4 (Z)-omDASS之X-ray晶體結構 43 2-3 化合物omDASS之VT-NMR分析旋轉運動 47 2-3.1 化合物 (E)-omDASS之VT-NMR分析 47 2-3.2 化合物 (Z)-omDASS之VT-NMR分析 50 2-4 目標化合物之吸收光譜圖 54 2-4.1 mmDASS之吸收光譜圖 54 2-4.2 omDASS之吸收光譜圖 55 2-5 目標化合物之螢光光譜圖 57 2-5-1 mmDASS之螢光光譜圖 57 2-5-2 omDASS之螢光光譜圖 58 2-6 光異構化特性 60 2-6.1 化合物 (E)-mmDASS之光異構化實驗 60 2-6.2 化合物 (E)-omDASS之光異構化實驗 62 2-7 化合物之自由旋轉子效應 66 2-7-1 設計概念 66 2-7-2 自由旋轉子效應實驗之結果與討論 67 2-7-2.1 化合物 (E)-omDASS之自由旋轉子效應 67 2-7-2.2 化合物 (E)-mmDASS之自由旋轉子效應 69 第三章 結論 72 第四章 實驗藥品、儀器與方法 74 4-1 實驗藥品與溶劑 74 4-2 實驗儀器與方法 76 4-2-1 螢光量子產率之測量步驟 78 4-2-2 異構化量子產率之測量步驟 79 4-2-2.1 (Z)-mmDASS之光異構化量子產率量測 81 4-2-2.2 (E)-omDASS之光異構化量子產率量測 86 4-2-2.3 化合物之消光係數測量 90 4-3 實驗之黏滯度參數 91 4-4 化合物合成步驟 92 參考資料 101 附圖 107 附錄 (oo-DASS) 151 附-1 化合物 (E)-ooDASS之合成 151 附-2 (E)-ooDASS之X-ray晶體結構 153 附-3 (E)-ooDASS之吸收光譜圖 154 附-4 化合物合成步驟 155 附錄圖 157 | |
dc.language.iso | zh-TW | |
dc.title | 雙胺基取代剛性二苯乙烯系統之光物理性質及扭轉運動之探討 | zh_TW |
dc.title | Photophysical Properties and Torsional Motions of Bis-Amino Substituted Stiff-Stilbene System | en |
dc.type | Thesis | |
dc.date.schoolyear | 108-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 蔡蘊明(Yeun-Min Tsai),林哲仁(Che-Jen Lin),何郡軒(Jinn-Hsuan Ho) | |
dc.subject.keyword | 剛性二苯乙烯,扭轉運動,異構化機制,間位胺基效應,螺旋反轉, | zh_TW |
dc.subject.keyword | stiff-stilbene,isomerization mechanism,helical inversion,meta amino effect, | en |
dc.relation.page | 168 | |
dc.identifier.doi | 10.6342/NTU202003526 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2020-08-26 | |
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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