Citation: SUN Qian, WANG Jin-Ting, ZHANG Li-Min, YANG Mao-Ping. Photoinduced Electron and Hydrogen Transfer Reactions of Thioxanthone with Amines, Phenols and Alcohols[J]. Acta Physico-Chimica Sinica, ;2010, 26(09): 2481-2488. doi: 10.3866/PKU.WHXB20100925 shu

Photoinduced Electron and Hydrogen Transfer Reactions of Thioxanthone with Amines, Phenols and Alcohols

1.
Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China

Received Date: 12 April 2010
Available Online: 19 July 2010
Fund Project: 国家自然科学基金(20673108)资助项目 (20673108)

The quenching reactions of triplet thioxanthone (TX) by a series of amines, phenols, and alcohols were investigated by laser flash photolysis in deoxygenated acetonitrile. We obtained corresponding transient absorption spectra and quenching rate constants (k_q). Fromchanges in the transient absorption spectra, we determine that the electron transfer reactions occur between triplet TX and amines without an active hydrogen while electron/proton transfer reactions occur between triplet TX and amines with an active hydrogen. The appearance of hydrogenated radicals can be regarded as evidence for hydrogen transfer reactions in the TX/phenol and TX/alcohol systems. In the TX/amine systems, the quenching rate constants decreased with an increase in the free energy change (ΔG). This indicates that electron transfer reactions influence the quenching of triplet TX. In the TX/phenol systems, the quenching rate constants decreased with an increase in ΔG firstly, then increased with an increase in phenol cation acidity. This can be explained by considering that charge transfer and hydrogen transfer may play separate but important roles. In the TX/ alcohol system, the quenching rate constants decreased with an increase in the α-C—H bonding energy of alcohols, and this indicates that the α-C—H bonding energy is a key factor during triplet TX quenching. By comparison with previous studies about the quenching reactions of triplet xanthone (XT) and fluorenone (FL) by a series of amines, phenols, and alcohols, it is established that because of a discrepancy in molecular configurations the quenching rate constants decrease according to the following order: XT, TX, and FL.
- Electron transfer,
- Hydrogen transfer,
- Thioxanthone,
- Amines,
- Phenols
1. [1]
  
  1. Morlet-Savary, F.; Ley, C.; Jacques, P.; Wieder, F.; Fouassier, J. P. J. Photochem. Photobiol. A-Chem., 1999, 126: 7
2. [2]
  2. Allonas, X.; Ley, C.; Bibaut, C.; Jacques, P.; Fouassier, J. P. Chem. Phys. Lett., 2000, 322: 483
3. [3]
  3. Okano, L. T.; Barros, T. C.; Chou, D. T. H.; Bennet, A. J. J. Phys. Chem. B, 2001, 105: 2122
4. [4]
  4. Satzger, H.; Schmidt, B.; Root, C.; Zinth, W.; Fierz, B.; Krieger, F.; Kiefhaber, T.; Gilch, P. J. Phys. Chem. A, 2004, 108: 10072
5. [5]
  5. Zhu, Q. Q.; Schnabel, W. J. Chem. Soc. Faraday Trans., 1991, 87: 1531
6. [6]
  6. Yates, S. F.; Schuster, G. B. J. Org. Chem., 1984, 49: 3349
7. [7]
  7. Inbar, S.; Linschitz, H.; Cohen, S. G. J. Am. Chem. Soc., 1980, 102: 1419
8. [8]
  8. Guttenplan, J. B.; Cohen, S. G. J. Am. Chem. Soc., 1972, 94: 4040
9. [9]
  9. Simon, J. D.; Peters, K. S. J. Am. Chem. Soc., 1981, 103: 6403
10. [10]
  10. Wang, J. T.; Pan, Y.; Zhang, L. M.; Yu, S. Q. Chinese Journal of Chemical Physics, 2007, 20: 395 [王金婷,潘洋, 张立敏, 俞书勤.化学物理学报, 2007, 20: 395 ]
11. [11]
  11. Stevenson, J. P.; DeMaria, D.; Reilly, D.; Purvis, J. D.; Graham, M. A.; Lockwood, G.; Drozd, M.; O忆Dwyer, P. J. Cancer Chemother. Pharmacol., 1999, 44: 228
12. [12]
  12. Izbicka, E.; Lawrence, R.; Davidson, K.; Rake, J. B.; VonHoff, D. D. Invest. New Drugs, 1999, 16: 221
13. [13]
  13. Pan, Y.; Fu ,Y.; Liu, S. X.; Yu, H. Z.; Gao, Y. H.; Guo, Q. X.; Yu, S. Q. J. Phys. Chem. A, 2006, 110: 7316
14. [14]
  14. Dalton, J. C.; Mont mery, F. C. J. Am. Chem. Soc., 1974, 96: 6230
15. [15]
  15. Ferreira, G. C.; Schmitt, C. C.; Neumann, M. G. J. Braz. Chem. Soc., 2006, 17: 905
16. [16]
  16. Scigalski, F.; Paczkowski, J. Macromol. Chem. Phys., 2008, 209: 1872
17. [17]
  17. Das, D.; Nath, D. N. J. Phys. Chem. A, 2008, 112: 11619
18. [18]
  18. Bordwell, F. G.; Cheng, J. P. J. Am. Chem. Soc., 1991, 113: 1736
19. [19]
  19. Denisov, E. T.; Denisova, T. G. Handbook of antioxidants. Boca Raton: CRC Press, 2000: 24
20. [20]
  20. Wang, J. T. Laser flash photolysis studies on some organic molecules [D]. Hefei: University of Science and Technology of China, 2009 [王金婷.若干有机分子的激光闪光光解研究[D]. 合肥:中国科学技术大学, 2009]
21. [21]
  21. Pan, Y.; Sheng, Z. Y.; Ye, X. D.; Ao, Z.; Yu, S. Q. J. Photochem. Photobiol. A-Chem., 2005, 174: 98
22. [22]
  22. Pan, Y.; Sheng, Z. Y.; Li, J.; Dai, J. H.; Chu, G. S.; Yu, S. Q. Acta Chim. Sin., 2004, 62: 1293 [潘洋, 盛震宇,李江,戴静华, 储高升, 俞书勤.化学学报, 2004, 62: 1293]
23. [23]
  23. Murov, S. L.; Carmichael, I.; Hug, G. Handbook of photochemistry. 2nd ed. NewYork: Marcel Dekker, 1993: 111, 346-348
24. [24]
  24. Corrales, T.; Peinado, C.; Catalina, F.; Neumann, M. G.; Allen, N. S.; Rufs, A. M.; Encinas, M. V. Polymer, 2000, 41: 9103
25. [25]
  25. Bartholomew, R. F.; Davidson, R. S.; Lambeth, P. F.; Mckellar, J. F.; Turner, P. H. J. Chem. Soc. Perkin Trans., 1972, 2: 577
26. [26]
  26. Das, P. K.; Encinas, M. V.; Steenken, S.; Scaiano, J. C. J. Am. Chem. Soc., 1981, 103: 4162
27. [27]
  27. Yoshihara, T.; Yamaji, M.; Itoh, T.; Shizuka, H.; Shimokage, T.; Tero-Kubota, S. Phys. Chem. Chem. Phys., 2000, 2: 993
28. [28]
  28. Rehm, D.; Weller, A. Isr. J. Chem., 1970, 8: 259
29. [29]
  29. Bard, A. J.; Faulkner, L. R. Electrochemical methods, fundamentals and applications. NewYork: John Wiley, 1980: 701
30. [30]
  30. (a) Nocera, D. G.; Gray, H. B. J. Am. Chem. Soc., 1981, 103: 7349 (b) Dvorak, V.; Nemec. I.; Zyka, J. J. Microchem. J., 1967, 12: 99 (c) Pan, Y.; Tang, W. J.; Yu, T. Q.; Wang, J. T.; Fu, Y.; Wang, G. W.; Yu, S. Q. J. Lumin., 2007, 126: 421 (d) Nelsen, S. F.; Hinz, P. J. J. Am. Chem. Soc., 1972, 94: 7114
31. [31]
  31. Herkatroeter, W. G.; Lamula, A. A.; Hammond, G. S. J. Am. Chem. Soc., 1964, 86: 4537
32. [32]
  32. Cao, X. Z.; Song, T. Y.;Wang, X. Q. Inorganic chemistry. 3rd ed. Beijing: Higher Education Press, 1994: 114-116 [曹锡章, 宋天佑,王杏乔.无机化学.北京:高等教育出版社, 1994: 114-116]
1. [1]
  Yi Yang , Xin Zhou , Miaoli Gu , Bei Cheng , Zhen Wu , Jianjun Zhang . Femtosecond transient absorption spectroscopy investigation on ultrafast electron transfer in S-scheme ZnO/CdIn₂S₄ photocatalyst for H₂O₂ production and benzylamine oxidation. Acta Physico-Chimica Sinica, 2025, 41(6): 100064-0. doi: 10.1016/j.actphy.2025.100064
2. [2]
  Jinfu Ma , Hui Lu , Jiandong Wu , Zhongli Zou . Teaching Design of Electrochemical Principles Course Based on “Cognitive Laws”: Kinetics of Electron Transfer Steps. University Chemistry, 2024, 39(3): 174-177. doi: 10.3866/PKU.DXHX202309052
3. [3]
  Lele Feng , Xueying Bai , Jifeng Pang , Hongchen Cao , Xiaoyan Liu , Wenhao Luo , Xiaofeng Yang , Pengfei Wu , Mingyuan Zheng . Single-atom Pd boosted Cu catalysts for ethanol dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(9): 100100-0. doi: 10.1016/j.actphy.2025.100100
4. [4]
  Weicheng Feng , Jingcheng Yu , Yilan Yang , Yige Guo , Geng Zou , Xiaoju Liu , Zhou Chen , Kun Dong , Yuefeng Song , Guoxiong Wang , Xinhe Bao . Regulating the High Entropy Component of Double Perovskite for High-Temperature Oxygen Evolution Reaction. Acta Physico-Chimica Sinica, 2024, 40(6): 2306013-0. doi: 10.3866/PKU.WHXB202306013
5. [5]
  Jizhou Liu , Chenbin Ai , Chenrui Hu , Bei Cheng , Jianjun Zhang . Accelerated Interfacial Electron Transfer in Perovskite Solar Cell by Ammonium Hexachlorostannate Modification and fs-TAS Investigation. Acta Physico-Chimica Sinica, 2024, 40(11): 2402006-0. doi: 10.3866/PKU.WHXB202402006
6. [6]
  Jiajie Cai , Chang Cheng , Bowen Liu , Jianjun Zhang , Chuanjia Jiang , Bei Cheng . CdS/DBTSO-BDTO S-scheme photocatalyst for H₂ production and its charge transfer dynamics. Acta Physico-Chimica Sinica, 2025, 41(8): 100084-0. doi: 10.1016/j.actphy.2025.100084
7. [7]
  Weilai Yu , Chuanbiao Bie . Unveiling S-Scheme Charge Transfer Mechanism. Acta Physico-Chimica Sinica, 2024, 40(4): 2307022-0. doi: 10.3866/PKU.WHXB202307022
8. [8]
  Qi Wu , Changhua Wang , Yingying Li , Xintong Zhang . Enhanced photocatalytic synthesis of H₂O₂ by triplet electron transfer at g-C₃N₄@BN van der Waals heterojunction interface. Acta Physico-Chimica Sinica, 2025, 41(9): 100107-0. doi: 10.1016/j.actphy.2025.100107
9. [9]
  Weikang Wang , Yadong Wu , Jianjun Zhang , Kai Meng , Jinhe Li , Lele Wang , Qinqin Liu . Green H₂O₂ synthesis via melamine-foam supported S-scheme Cd_0.5Zn_0.5In₂S₄/S-doped carbon nitride heterojunction: synergistic interfacial charge transfer and local photothermal effect. Acta Physico-Chimica Sinica, 2025, 41(8): 100093-0. doi: 10.1016/j.actphy.2025.100093
10. [10]
  Zhongyan Cao , Shengnan Jin , Yuxia Wang , Yiyi Chen , Xianqiang Kong , Yuanqing Xu . Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors. University Chemistry, 2025, 40(4): 245-252. doi: 10.12461/PKU.DXHX202405186
11. [11]
  Jiajia Li , Xiangyu Zhang , Zhihan Yuan , Zhengyang Qian , Jian Zhu . 3D Printing Based on Photo-Induced Reversible Addition-Fragmentation Chain Transfer Polymerization. University Chemistry, 2024, 39(5): 11-19. doi: 10.3866/PKU.DXHX202309073
12. [12]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
13. [13]
  Yajuan Xing , Hui Xue , Jing Sun , Niankun Guo , Tianshan Song , Jiawen Sun , Yi-Ru Hao , Qin Wang . Cu₃P-Induced Charge-Oriented Transfer and Surface Reconstruction of Ni₂P to Achieve Efficient Oxygen Evolution Activity. Acta Physico-Chimica Sinica, 2024, 40(3): 2304046-0. doi: 10.3866/PKU.WHXB202304046
14. [14]
  Xuexia He , Zhibin Lei , Pei Chen , Qi Li , Weiyu Deng , Peng Hu . 以“溶度积规则”指导电荷转移共晶沉淀析出——材料类专业无机化学教学改革案例. University Chemistry, 2025, 40(8): 1-10. doi: 10.12461/PKU.DXHX202410099
15. [15]
  Yongqing Kuang , Jie Liu , Jianjun Feng , Wen Yang , Shuanglian Cai , Ling Shi . Experimental Design for the Two-Step Synthesis of Paracetamol from 4-Hydroxyacetophenone. University Chemistry, 2024, 39(8): 331-337. doi: 10.12461/PKU.DXHX202403012
16. [16]
  Peng Li , Yuanying Cui , Zhongliao Wang , Graham Dawson , Chunfeng Shao , Kai Dai . Efficient interfacial charge transfer of CeO₂/Bi₁₉Br₃S₂₇ S-scheme heterojunction for boosted photocatalytic CO₂ reduction. Acta Physico-Chimica Sinica, 2025, 41(6): 100065-0. doi: 10.1016/j.actphy.2025.100065
17. [17]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 2309027-0. doi: 10.3866/PKU.WHXB202309027
18. [18]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . Efficient Photocatalytic Production of H₂O₂ over ZnO/D-A Conjugated Polymer S-scheme Heterojunction and Charge Transfer Dynamics Investigation. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-0. doi: 10.3866/PKU.WHXB202406027
19. [19]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029
20. [20]
  Xinyu Miao , Hao Yang , Jie He , Jing Wang , Zhiliang Jin . Adjusting the electronic structure of Keggin-type polyoxometalates to construct S-scheme heterojunction for photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2025, 41(6): 100051-0. doi: 10.1016/j.actphy.2025.100051

Get Citation

PDF

XML

Metrics

PDF Downloads(1127)
Abstract views(2972)
HTML views(12)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142