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論文名稱(中文) 2-(2’-羥基-5’-甲基苯基)苯駢三唑的碳-11位上拉電子基衍生物之合成、光物理及理論計算探討
論文名稱(英文) Synthesis, Photophysics and Computation of 2-(2’-hydroxyl- 5’-methylphenyl)benzotriazole (TIN P) Derivatives with the Electron-Withdrawing Groups at C-11 Position
校院名稱 成功大學
系所名稱(中) 化學系碩博士班
系所名稱(英) Department of Chemistry
學年度 100
學期 2
出版年 101
研究生(中文) 許峻嘉
研究生(英文) Chun-Chia Hsu
學號 l36991166
學位類別 碩士
語文別 中文
論文頁數 196頁
口試委員 指導教授-黃守仁
口試委員-黃福永
口試委員-王小萍
中文關鍵字 分子內氫鍵  密度泛函理論  立體礙障  激發態分子內質子轉移  分子內電荷轉移  紫外光吸收  螢光  拉電子官能基 
英文關鍵字 Tinuvin P  IMHB  density functional theory  steric effect  ESIPT  ICT  UV absorption  Fluorescence  electron withdraw group 
學科別分類
中文摘要 本實驗利用紫外光吸收劑2-(2’-羥基-5’-甲基苯基)苯并三唑 (1) 為起始物合成2-(2’-羥基-5’-甲基-3’-硝基苯基)苯并三唑 (2) 、 2-(2’-羥基-5’-甲基-3’-磺酸苯基)苯并三唑 (3) 、 2-(2’-羥基-3’-甲氧基甲基-5’-甲基苯基)苯并三唑 (4) 、 2-(2’-羥基-3’-甲氧基甲基-5’-甲基苯基)苯并三唑 (4) 、 2-(2’-羥基-3’-丁氧基甲基-5’-甲基苯基)苯并三唑 (5) 及2-(2’-甲氧基-5’-甲基苯基)苯并三唑 (6) 等衍生物。溶於正己烷、環己烷、甲醇及二甲基亞碸溶媒中,以溶液態測定衍生物光物理性質(紫外-可見光、螢光),探討其在溶液態時的紫外光吸收、螢光放射等行為,理論計算採用密度泛函理論方法驗證並解釋實驗結果。根據紫外光吸收及螢光結果推測在C-11位置上改為拉電子官能基的化合物可提升分子內氫鍵強度且化合物(4)、(5) 因取代基立體障礙能抵擋溶劑分子與化合物產生分子間氫鍵作用而造成化合物本身的分子內氫鍵破壞。當溶劑分子的極性提升易與化合物本身的氫氧基產生分子間氫鍵進而破壞分子內氫鍵造成長波長吸收峰(345 nm,屬於π->π* 電子躍遷)吸收值變弱。利用分子軌域合理分析化合物(1)-(5) 傾向發生在激發態進行分子內質子轉移,行激發態去活化行為。
英文摘要 In the present work, UV absorber, 2-(2’-hydroxyl-5’-methylphenyl) benzotriazole (1), has been taken as the starting material to synthesize various derivatives such as 2-(2’-hydroxyl-5’-methyl-3’-nitrophenyl) benzotriazole (2), 2-(2’-hydroxyl-5’-methyl-3’-sulfonphenyl)benzotriazole (3), 2-(2’-hydroxyl-3’- methoxymethyl-5’-methylphenyl)benzotriazole (4), 2-(2’-hydroxyl- 3’-butoxy- methyl-5’-methylphenyl)benzotriazole (5) and 2-(2’-methoxy- 5’-methylphenyl) benzotriazole (6). Each of the derivatives was dissolved in hexane, cyclohexane, methanol and DMSO, respectively, to measure the photophysical properties (UV/Vis and Fluorescence). Spectroscopic study of UV/Vis absorption and fluorescence emission in solution state, and theoretical study with density functional theory (DFT) method were employed to characterize these UV absorbers. According to the results of UV absorption and fluorescence emission, it was found compounds with electron- withdrawing groups in the C-11 site could promote the strength of intramolecular hydrogen bonding and compounds (4,5) were capable of preventing from interacting with the solvent, which was due to the steric effect from bulkyl substituent in the C-11 site. By using molecular orbital analysis, it was found we can reasonably analyze that compounds(1)-(5) prefer intramolecular proton transfer in excited state (1) to (5) as to deactivate the excited state.
論文目次 中文摘要 ------------------------------- I
英文摘要 ------------------------------- II
誌謝 ------------------------------- III
目錄 ------------------------------- V
圖目錄 ------------------------------- VII
表目錄 ------------------------------- XII
第一章 緒論-------------------------- 1
1-1 前言----------------------- 1
1-2 Tinuvin P介紹及型態--------- 4
1-3 研究動機------------------- 5
第二章 相關研究回顧------------------- 7
2-1 TIN P製備文獻回顧----------- 7
2-2 TIN P衍生物文獻回顧--------- 12
2-3 實驗及理論文獻回顧----------- 17
2-4 計算原理與方法-------------- 21
2-5 紫外線-可見光吸收光譜原理---- 28
2-6 螢光理論------------------- 31
第三章 實驗部分----------------------- 37
3-1 實驗儀器和藥品-------------- 37
3-2 TIN P衍生物之合成----------- 43
第四章 結果與討論--------------------- 48
4-1 TIN P衍生物之單晶結構------- 48
4-2 化合物之光學性質------------ 57
4-2-1 紫外-可見光吸收光譜----- 57
4-2-2 螢光放射光譜----------- 99
4-3 位能曲線------------------- 112
4-4 前鋒分子軌域---------------- 116
4-5 理論IR光譜----------------- 126
第五章 結論-------------------------- 129
參考文獻 ------------------------------- 132
附錄 ------------------------------- 138
附錄一 IR 光譜----------------- 138
附錄二 單晶結構數據------------- 155
附錄三 化合物NMR光譜------------ 180

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