本論文利用實驗室自行架設的飛秒瞬態吸收(transient absorption, TA)光譜儀及一套全自動數據擷取電腦程式，研究電子給體-受體(electron doner-acceptor, EDA)錯合物的分子間電子轉移動力學行為。研究對象為以苯(benzene)為電子給體，四氰基乙烯(tetracyanoethylene)為電子受體之EDA錯合物溶於不同比例之苯/二氯甲烷混合溶劑。在論文中，我們直接激發Bz/TCNE錯合物的電荷轉移(charge transfer, CT)態，觀察到四氰基乙烯自由基陰離子(TCNE-)與苯二聚體自由基陽離子((Bz)2+)的光譜特徵，及其時間變化之行為，並與實驗室前人研究激發溶於不同比例苯/四氯化碳混合溶劑的Bz/TCNE錯合物的CT態電子轉移動力學做比較。於TA光譜中，我們觀察到激發錯合物CT態後，激發態錯合物會先進行較快的溶劑及振動緩解，接著為較慢的電荷重合(charge recombination, CR)反應。我們發現電荷再結合過程的時間常數在二氯甲烷溶劑中比在四氯化碳溶劑中來的短，且此時間常數隨著苯/二氯甲烷混合溶液中苯的比例的變化趨勢與前人所報告之在苯/四氯化碳混合溶液中的結果有所不同。

In this thesis we study the charge-transfer (CT) dynamics of the electron donor-acceptor (EDA) complexes with a home-built broadband femtosecond transient absorption (TA) spectrometer. The EDA system studied here are benzene/tetracyanoethylene (Bz/TCNE) complexes dissolved in a series of Bz/Dichloromethane (Bz/DCM) cosolvents of different ratios. We directly excite the CT state of Bz/TCNE complexes in dichloromethane to observe their relaxation dynamics and compare the results with those of previously-studied Bz/TCNE complex in carbon tetrachloride. We observe spectral characteristics of TCNE radical anion (TCNE-) and benzene dimer radical cation ((Bz)2+). By analyzing their time-dependent behaviors, we found that after exciting the CT state of Bz/TCNE complexes, the excited state undergoes rapid solvation and vibrational relaxation, followed by a slower charge recombination (CR) reaction. We found that the time constant of the CR process is shorter in the dichloromethane solvent than in the carbon tetrachloride solvent. The variation of the CR time constant with the benzene ratio in the Bz/DCM cosolvents is different from that observed in Bz/CCl4 cosolvents.

摘要 i
Abstract ii
目錄 iii
圖目錄 v
表目錄 viii

第一章 序論 1
1.1 電子轉移概論 1
1.2 電子轉移理論 3
1.3 EDA錯合物簡介 6
1.4 苯/四氰基乙烯錯合物電子轉移動力學回顧 6
1.5 論文研究目的 9

第二章 實驗系統與技術 10
2.1超快飛秒雷射系統 10
2.1.1 飛秒雷射產生源 11
2.1.2 能量再生放大器 15
2.2 飛秒瞬態吸收光譜 20
2.2.1 原理 20
2.2.2 390 nm激發瞬態吸收光譜光路架設 22
2.2.3 瞬態吸收光譜自動化數據擷取系統 24
2.2.4 儀器響應函數 27
2.2.5 瞬態吸收光譜時間延遲校正 28
2.2.6 瞬態吸收光譜背景校正 30
2.3 實驗藥品與EDA錯合物配置 34
第三章 以飛秒瞬態吸收光譜研究苯/四氰基乙烯在二氯甲烷中電子轉移態電荷轉移動力學 35
3.1 Bz/TCNE錯合物在二氯甲烷中之CT態靜態吸收光譜 35
3.2 Bz/TCNE錯合物在二氯甲烷中電荷轉移態瞬態吸收光譜 40
3.2.1 Bz/TCNE錯合物在不同比例Bz/DCM混合溶劑中的瞬態吸收光譜 40
3.2.2 450±2 nm (TCNE-)光區瞬態吸收動力學過程討論 51
3.2.3 850±12 nm光區((Bz)2+)瞬態吸收動力學過程討論 54
3.3綜合討論 59
3.3.1 二氯甲烷中Bz/TCNE錯合物CT態的衰減動力學討論 59
3.3.2 在DCM與CCl4中Bz/TCNE錯合物CT態的衰減動力學比較 59

第四章 結論 63

附錄 66
附錄一 390 nm激發動力學模型擬合過程 66

Reference 68

1. Ho, Hon Eong; Pagano, Angela; Rossi-Ashton, James A.; Donald, James R.; Epton, Ryan G.; Churchill, Jonathan C.; James, Michael J.; O'Brien, Peter; Taylor, Richard J. K.; Unsworth, William P. Visible-light-induced intramolecular charge transfer in the radical spirocyclisation of indole-tethered ynones. Chemical Science , 2020, 11, 1353-1360
2. Philip, A. M., Hsu, C. C., Wei, Z., Fridriksson, M. B., Grozema, F. C., & Jager, W. F., Directing charge transfer in perylene based light-harvesting antenna molecules. J. Chem. Phys, 153, 144302 (2020)
3. Fukuzumi, S., New perspective of electron transfer chemistry. J Organic biomolecular chemistry, 2003, 1 (4), 609-620.
4. Taube, H., Recent progress in the study of inner-sphere electron transfer reactions. J PureApplied Chemistry, 1970, 24 (2), 289-306.
5. Barbara, P. F.; Meyer, T. J.; Ratner, M. A., Contemporary issues in electron transfer research. J The Journal of Physical Chemistry 1996, 100 (31), 13148-13168.
6. Kuznetsov, A. M.; Ulstrup, J., Electron transfer in chemistry and biology. Wiley, Chichester: 1999.
7. Weller, A., Exciplex and radical pairs in photochemical electron transfer. J Pure Applied Chemistry, 1982, 54 (10), 1885-1888.
8. Rehm, D.; Weller, A., Kinetics of fluorescence quenching by electron and H‐atom transfer. J Israel Journal of Chemistry, 1970, 8 (2), 259-271.
9. Chakrabarty, D.; Seth, D.; Chakraborty, A.; Sarkar, N., Dynamics of solvation and rotational relaxation of coumarin 153 in ionic liquid confined nanometer-sized microemulsions. J The Journal of Physical Chemistry B, 2005, 109 (12), 5753-5758.
10. Ghosh, S.; Mondal, S. K.; Sahu, K.; Bhattacharyya, K., Ultrafast electron transfer in a nanocavity. Dimethylaniline to coumarin dyes in hydroxypropyl γ-cyclodextrin. J The Journal of Physical Chemistry A, 2006, 110 (49), 13139-13144.
11. Morandeira, A.; Fürstenberg, A.; Pagès, S.; Lang, B.; Vauthey, E., Ultrafast spectroscopy on bimolecular photoinduced electron transfer reactions. J Spectrum, 2004, 17 (4), 15.
12. Marcus, R. A., On the theory of oxidation‐reduction reactions involving electron transfer. I., J The Journal of Physical Chemistry, 1956, 24 (5), 966-978.
13. Kroon, J.; Oevering, H.; Verhoeven, J. W.; Warman, J. M.; Oliver, A. M.; Paddon-Row, M. N., Temperature effects on intramolecular electron transfer kinetics under" normal"," inverted", and" nearly optimal" conditions. J The Journal of Physical Chemistry, 1993, 97 (19), 5065-5069.
14. Miller, J. R.; Calcaterra, L.; Closs, G., Intramolecular long-distance electron transfer in radical anions. The effects of free energy and solvent on the reaction rates. J Journal of the American Chemical Society, 1984, 106 (10), 3047-3049.
15. Mulliken, R. S., Molecular compounds and their spectra. III. The interaction of electron donors and acceptors. J The Journal of Physical Chemistry, 1952, 56 (7), 801-822.
16. Chiu, C.-C.; Hung, C.-C.; Chen, C.-L.; Cheng, P.-Y., Ultrafast Time-Resolved Broadband Fluorescence Studies of the Benzene-Tetracyanoethylene Complex: Solvation, Vibrational Relaxation, and Charge Recombination Dynamics. J The Journal of Physical Chemistry B, 2013, 117 (33), 9734-9756.
17. Chiu, C.-C.; Hung, C.-C.; Cheng, P.-Y., Ultrafast Charge Recombination Dynamics in Ternary Electron Donor–Acceptor Complexes:(Benzene) 2-Tetracyanoethylene Complexes. J The Journal of Physical Chemistry B, 2016, 120 (48), 12390-12403.
18. 廖翊凱. 以飛秒瞬態吸收光譜研究苯/四氰基乙烯錯合物之電荷轉移態與局部激發態之電荷轉移動力學. 國立清華大學化學所碩士論文, 2019.
19. Smith, M. L.; McHale, J. L., Optical and resonance Raman studies of the 1: 1 and 2: 1 complexes of hexamethylbenzene with tetracyanoethylene. J The Journal of Physical Chemistry, 1985, 89 (19), 4002-4007.
20. Merriam, M.; Rodriguez, R.; McHale, J. L., Charge-transfer transitions of 2: 1 electron donor-acceptor complexes. J Journal of Physical Chemistry, 1987, 91 (5), 1058-1063.
21. Ho, Y. E.; Thompson, C. C. J. J. o. t. C. S., Chemical Communications, Termolecular complexes of tetracyanoethylene with weak electron donors. Journal of the Chemical Society, Chemical Communications, 1973, (17), 609-610.
22. Foster, R.; Kulevsky, N., Dipole moment of a termolecular charge-transfer complex. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1973, 69, 1427-1431.
23. Kysel, O.; Juhász, G.; Mach, P.; Košík, G., Theoretical study of solvent effect on π-EDA complexation II. Complex between TCNE and two benzene molecules. J Chemical Papers, 2007, 61 (1), 66-72.
24. Nakai, Y.; Ohashi, K.; Nishi, N., Electronic structures and photoevaporation dynamics of benzene cluster ions. J The Journal of Physical Chemistry A, 1997, 101 (4), 472-480.
25. Mukherjee, A.; Lavery, R.; Bagchi, B.; Hynes, J. T., On the molecular mechanism of drug intercalation into DNA: a simulation study of the intercalation pathway, free energy, and DNA structural changes. J Journal of the American Chemical Society, 2008, 130 (30), 9747-9755.
26. Lorenc, M.; Ziolek, M.; Naskrecki, R.; Karolczak, J.; Kubicki, J.; Maciejewski, A., Artifacts in femtosecond transient absorption spectroscopy. J Applied Physics B, 2002, 74 (1), 19-27.
27. Wynne, K.; Galli, C.; Hochstrasser, R., Ultrafast charge transfer in an electron donor–acceptor complex. J The Journal of chemical physics, 1994, 100 (7), 4797-4810.
28. Frey, J. E.; Andrews, A. M.; Ankoviac, D. G.; Beaman, D. N.; Du Pont, L. E.; Elsner, T. E.; Lang, S. R.; Zwart, M. A. O.; Seagle, R. E.; Torreano, L. A., Charge-transfer complexes of tetracyanoethylene with cycloalkanes, alkenes, and alkynes and some of their aryl derivatives. J The Journal of Organic Chemistry, 1990, 55 (2), 606-624.
29. Jeanmaire, D. L.; Suchanski, M. R.; Van Duyne, R. P., Resonance Raman spectroelectrochemistry. I. Tetracyanoethylene anion radical. J Journal of the American Chemical Society, 1975, 97 (7), 1699-1707.
30. Inokuchi, Y.; Naitoh, Y.; Ohashi, K.; Saitow, K.-i.; Yoshihara, K.; Nishi, N., Formation of benzene dimer cations in neat liquid benzene studied by femtosecond transient absorption spectroscopy. J Chemical physics letters, 1997, 269 (3-4), 298-304.