記
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4212
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NC091FJU00065008
態
助
教
查
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索
書
號
學
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輔仁大學
名
稱
系
所
化學系
名
稱
舊
系
所
名
稱
學
488338013
號
研
究
生 鄭仲志
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中
)
研
究
Chung-Chih Cheng
生
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英
)
論
文
名
稱 分子內以及主/客體型式激發態質子轉移與電荷轉移之研究
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中
)
論
文
名
稱 The Intramolecuar and Host/Guest Type of Excited-State Proton Transfer and Charge Transfer Reactions
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英
)
其
他
題
名
指
導
教
授 張鎮平 周必泰
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中
)
指
導
教
授 Chen-Pin Chang Pi-Tai Chou
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英
)
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01
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學
位
博士
類
別
畢
業
學 91
年
度
出
版
年
語
文 英文
別
關
鍵
字
激發態質子轉移 激發態電荷轉移 分子間 分子內 主/客體
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中
)
關
鍵
字 Excited-State Proton Transfer Excited-State Change Transfer Intramolecular Intermolecular Host/Guest
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英
)
摘
要
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中
)
中文摘要 在這四年博士班歷程中，我的主要研究領域是激發態質子轉移光譜及動力學，這中間又包含
力學、激發態雙氫鍵轉移的光譜及動力學，並藉由質子給予及接受官能基的不同距離及幾何效應來探
移及電子轉移的特性，我們更在探討緩解動力學中解析出這兩者間的不同。為了給予第二、三章節甚
四章是我最近剛完成的研究工作，第四章主要在探討弱氫鍵系統的激發態質子轉移效應，這一方面的
分發揮，來描述其反應位能曲面，故這新系統的開發對未來質子反應動力學的影響將是無遠弗屆。 再
摘 Abstract Contemporary progress regarding guest/host types of excited-state double proton-transfer has been
要 proton transfer. Of particular emphases are the photophysical and photochemical properties of excited-state d
( and reviewed separately. For the case of static host/guest hydrogen-bonded complexes both hydrogen-bondin
英 transfer reaction in the non-catalytic host/guest type of ESDPT. The mechanisms of protic solvent assisted E
) water, aiming at its future perspective in biological applications. Finally, the differentiation in mechanism be
tautomerism for b-carboline (b-CB) and its analogues has been investigated. Thermodynamics and microsolv
of the stoichiometric ratio and structure for the hydrogen-bonding formation was provided by molecular desi
with time-resolved measurements and theoretical approaches suggest the 1:2 b-CB/acetic acid complex with
ps, indicating that only a negligibly small geometry adjustment is required for the guest molecule (i.e. acetic
tautomerism is prohibited during the excited-state lifetime, giving rise to a normal Stokes shifted emission. T
Comprehensive spectroscopic and dynamical studies on the dual excitation behavior of proton vs charge tran
high as ~ 4.2 x 10E3 and 5.2x10E4 M-1 (e.g., the DPP/acetic acid complex) at 298 K, respectively, which up
Stokes shifted emission band originates from the charge-transfer species incorporating a dimethylamine and
charge-transfer properties such as dipole moment, orbital configuration, etc. Supplementary support for the d
common Franck-Condon excited state but undergo two independent relaxation channels. In protic solvents, s
be distinguished via the temporal spectral evolution. The results demonstrate DPP to be a unique model amo
transfer (ESIrPT) and excited-state intermolecular proton-transfer (ESIePT) reactions in 5-membered N-H--which ESIrPT takes place with relatively slow rate of > 6 x10E11 s-1) of ESIePT, resulting in an imine/amin
between ESIrPT and ESIePT with their associated different spectral and relaxation dynamics makes 1a-d sys
論
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Table of Contents 中文摘要 Abstract Sub-Abstract (Chapter 2) Sub-Abstract (Chapter 3) Sub-Abstract (Cha
state proton transfer 2. Catalytic and noncatalytic host/guest ESDPT process 2.1. Conjugated dual hydrogen
through the covalent bond 3. Solvent Polarity coupled proton transfer reaction References Tables and Figure
3.2. Fluorescence Titration Study 4. Discussion 4.1. b-CD/Acetic Acid HB Structures 4.2. Theoretical Appro
amino)-1H-pyrrolo[2, 3-b]pyridines 112 1.Introduction 2. Experimental 2.1. Materials 2.2. Mesurements 3. R
in Aprotic Solvents 5. Conclusion References Tables and Figures Chapter 4. Excited-State Intra- and Intermo
Spectroscopy and Dynamics of ESIrPT 3.2. Spectroscopy and Dynamics of ESIePT 4. Conclusion Reference
參
考
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獻
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