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研究生： 吳念勳
Wu, Nien-Hsun
論文名稱： 以飛秒時間解析螢光光譜研究 3-氰基-4-甲基-7-羥基香豆素錯合物之 激發態質子轉移反應
Excited-State Proton Transfer Reaction in 3-Cyano-4-Methyl-7-Hydroxycoumarin Complexes Studied by Femtosecond Time-resolved Fluorescence Spectroscopy
指導教授： 鄭博元
Cheng, Po-Yuan
口試委員: 朱立岡
Chu, Li-Kang
高雅婷
Kao, Ya-ting
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2017
畢業學年度： 105
語文別： 中文
論文頁數： 112
中文關鍵詞： 激發態質子轉移 、化學動力學
外文關鍵詞： excited--state proton transfer, reaction dynamics
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    • 本論文以具有質子給體之3-氰基-4-甲基-7-羥基香豆素(3-Cyano-4-methyl-7-hydroxycoumarin,3CN4MU)作為研究分子，使其與不同質子親和力的質子受體N-甲基咪唑(1-Methyl Imidazole,1MI)或三乙基胺(Triethylamine,TEA)形成氫鍵錯合物，並比較此錯合物在不同極性溶劑中的激發態質子轉移行為。我們使用靜態吸收光譜、靜態螢光光譜以及奈秒時間解析螢光光譜得到其光譜特徵，再以實驗室自行架設之超快時間解析光學克爾光閘螢光光譜(ultrafast time-resolved optical Kerr gating fluorescence spectroscopy)取得時間解析螢光光譜，並以密度泛函理論(density functional theory)計算3CN4MU錯合物於激發前後的構型變化。綜合各項實驗及計算結果指認錯合物的不同構型，並討論其激發態質子轉移(excited state proton transfer, ESPT)。3CN4MU與較強質子親和力的TEA形成之錯合物於基態已發生質子轉移，因此無法有效觀察其ESPT現象。但在3CN4MU與較弱質子親和力的1MI之錯合物，實驗結果及理論計算均顯示為基態非質子轉移氫鍵錯合物。我們發現3CN4MU-1MI錯合物於非極性的甲苯中，溶劑分子無法透過solvation幫助錯合物質子轉移，因此在激發態質子轉移並不顯著。但在極性較高的乙酸乙酯溶液中，3CN4MU-1MI可藉由solvation幫助質子轉移，並有效地降低其自由能而穩定其分子，因此我們認為3CN4MU-1MI於乙酸乙酯溶液中可發生激發態質子轉移。在時間解析光譜中，我們以三個指數函數擬合全螢光強度P(t)，分別為0.6±0.3 ps、28±3 ps以及2290±50 ps。我們將0.6 ps指認為質子從3CN4MU轉移至1MI的第一步，為一solvation-controlled step，將28 ps指認為3CN4MU-1MI離子對進行進一步自身結構之調整，以降低整體離子對自由能之過程。2290 ps則為質子轉移離子對之激發態生命期。

    We studied intermolecular excited-state proton transfer (ESPT) dynamics in hydrogen-bonded complexes of 3-cyano-4-methyl-7-hydroxycoumarin (3CN4MU) by using steady-state absorption/fluorescence spectroscopy and ultrafast time-resolved optical Kerr gating fluorescence spectroscopy. Two different proton acceptors, 1-methyl imidazole (1MI) and triethylamine (TEA), were studied, and the experiments were carried out in strong- and weak-polarity solvents. We also carried out density-functional-theory (DFT) calculations to help us interpreting the experimental results.
    We found that 3CN4MU-TEA complex undergoes proton transfer in its ground state in both polar and non-polar solvents. In 3CN4MU-1MI complex, the proton transfer does not occur in ground state, as confirmed by experiments and DFT calculations. Due to the lack of solvation, ESPT in 3CN4MU-1MI complex can only partially occur in non-polar solvent. However, the ESPT of 3CN4MU-1MI complex occurs in polar solvent. We used a tri-exponential decay function to fit the total fluorescence intensity function (P(t)) and the time constants are 0.6±0.3ps, 28±3ps and 2290±50ps.The fastest component is assigned to the first step of ESPT, which is a solvation-controlled step. The second component is assigned to a structural relaxation which stabilizes the ion pair. The last one is the lifetime of the ESPT complex.

    第1章 序論 1 1.1 激發態質子轉移前言 1 1.2 激發態質子轉移理論 2 1.2.1 激發態質子轉移行為的時間尺度 2 1.2.2 photoacidity 2 1.3 羥基取代香豆素之研究回顧 6 1.4 本論文研究方法與目的 10 第2章 實驗系統與技術 13 2.1 超快飛秒雷射系統 13 2.1.1 雷射產生源 14 2.1.2 能量放大器 17 2.2 實驗技術 21 2.2.1 Optical Kerr Gating簡介 22 2.2.2 時間解析克爾光閘螢光光譜實驗系統與組成 23 2.2.3 超快時間解析克爾光閘螢光光譜實驗自動化數據擷取系統 34 2.3 時間解析克爾光閘螢光光譜儀的校正 37 2.3.1 光譜靈敏度的校正 37 2.3.2 時間延遲(temporal delay)校正 43 2.4 時間解析克爾光閘螢光光譜儀正確性探討 47 2.5 3CN4MU錯合物製備 48 第3章 結果與討論 51 3.1 3CN4MU氫鍵錯合物溶液的靜態光譜 51 3.1.1 3CN4MU氫鍵錯合物 51 3.1.2 3CN4MU - 1MI氫鍵錯合物之靜態光譜 52 3.1.3 3CN4MU -TEA氫鍵錯合物之靜態光譜 59 3.1.4 3CN4MU於水相之靜態光譜 63 3.1.5 靜態光譜整理 66 3.2 3CN4MU氫鍵錯合物之時間解析螢光光譜 70 3.2.1 3CN4MU於甲苯及乙酸乙酯之時間解析螢光光譜 70 3.2.2 3CN4MU-1MI於甲苯與乙酸乙酯時間解析螢光光譜 75 3.2.3 時間解析光譜整理 82 3.3 3CN4MU氫鍵錯合物及4MU氫鍵錯合物之理論計算 85 3.3.1 3CN4MU與4MU之單體及陰離子 85 3.3.2 3CN4MU-TEA氫鍵錯合物與4MU-TEA氫鍵錯合物 93 3.3.3 3CN4MU-1MI錯合物 101 3.3.4 3CN4MU與4MU之氫鍵討論 105 第4章 結論 109

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