Citation: 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[J]. Acta Physico-Chimica Sinica, ;2025, 41(2): 100012. doi: 10.3866/PKU.WHXB202309027 shu

Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone

1.
Key Laboratory of Advanced Light Conversion Materials and Biophotonics, Department of Chemistry, Renmin University of China, Beijing 100872, China;
2.
Information Technology Center, Renmin University of China, Beijing 100872, China;
3.
State Key Laboratory for Artificial Microstructure and Mesoscopic Physics, School of Physics, Peking University, Beijing 100871, China;
4.
State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China

Corresponding author: Peng Wang, wpeng_chem@ruc.edu.cn
Received Date: 15 September 2023
Revised Date: 26 October 2023
Accepted Date: 27 October 2023

Fund Project: The project was supported by the Fundamental Research Funds for the Central Universities, the Research Funds of Renmin University of China (21XNH085), and the Natural Science Foundation of China (21673289). The computer resources were provided by Public Computing Cloud Platform of Renmin University of China.

Excited-state intramolecular proton transfer (ESIPT) is a fundamental photoreaction of significant importance in both chemical and biological systems. This phenomenon typically occurs in chromophores featuring intramolecular hydrogen bonding. Among the molecules undergoing ESIPT, 3-hydroxyflavone derivatives (3-HFs) have garnered significant attention due to their natural origins and environmentally responsive fluorescence properties. A particular 3-HF compound, 4'-N,N-diethylamino-3-hydroxybenzoflavone (D-HBF), distinguished by its extended π-system and red-shifted electronic absorption, has recently been identified as a potent fluorescent probe highly sensitive to changes in environmental polarity. In this study, we systematically explored the ESIPT reaction mechanism of D-HBF in three aprotic solvents: cyclohexane, diethyl ether, and tetrahydrofuran, each possessing varying polarities. Our investigation involved a combination of spectroscopic and theoretical methods. In all three solvents, we observed the characteristic dual emission bands associated with ESIPT, with the intensity ratio of these bands being influenced by the solvent. As solvent polarity increased, we noted a decrease in the rates of both the forward and reverse proton transfer (PT) reactions based on our analysis of fluorescent kinetics. However, the reverse PT was favored. Through density functional theory (DFT) and time-dependent DFT (TDDFT) calculations of bond lengths and bond angles of the intramolecular hydrogen bond in these solvents, we confirmed that the ESIPT reaction in D-HBF is driven by the strengthening of the excited-state hydrogen bond. Notably, upon increasing solvent polarity, the intramolecular hydrogen bonds in the excited N* state weakened, as evidenced by the up-shifted IR absorption frequency of the O―H stretching mode in the S₁ state. Electron intensity analysis of frontier orbitals revealed characteristic intramolecular charge transfer (ICT) occurring in D-HBF upon photoexcitation, attributable to the introduction of a strong electron-donating group at the 4' position (4'-N,N-diethylamino-). Calculations of potential energy curves for the S₀ and S₁ states confirmed that the PT process tends to occur in the S₁ state rather than the S₀ state, and a more polar solvent generates a more significant potential barrier, hindering the corresponding ESIPT reaction. An analysis of the Gibbs free energy of ESIPT further confirmed that increasing solvent polarity favors the equilibrium shifting toward the N* state. This research lays the foundation for potential future applications of D-HBF as a biological fluorescent probe sensitive to environmental polarity.
- 4′-N,
- N-diethylamino-3-hydroxybenzoflavone,
- ESIPT,
- DFT/TD-DFT,
- Solvent polarity effect,
- Fluorescent dynamics
1. [1]
  (1) Kuang, Z.; Guo, Q.; Wang, X.; Song, H.; Maroncelli, M.; Xia, A. J. Phys. Chem. Lett. 2018, 9, 4174. doi: 10.1021/acs.jpclett.8b01826
2. [2]
  (2) Chen, Y.; Yang, Y.; Zhao, Y.; Liu, S.; Li, Y. Org. Chem. Front. 2019, 6, 218. doi: 10.1039/c8qo01111g
3. [3]
  (3) Skilitsi, A. I.; Agathangelou, D.; Shulov, L.; Conyard, J.; Haacke, S., Mély, Y.; Klymchenko, A.; Léonard, J. Phys. Chem. Chem. Phys. 2018, 20, 7885. doi: 10.1039/c7cp08584b
4. [4]
  (4) Chou, P.-T.; Martinez, M. L.; Clements, J. H. Chem. Phys. Lett. 1993, 204, 395. doi: 10.1016/0009-2614(93)89175-H
5. [5]
  (5) Qin, T.; Liu, B.; Huang, Y.; Yang, K.; Zhu, K.; Luo, Z.; Pan, C.; Wang, L. Sens. Actuators B-Chem. 2018, 277, 484. doi: 10.1016/j.snb.2018.09.056
6. [6]
  (6) Jiang, G.; Jin, Y.; Li, M.; Wang, H.; Xiong, M.; Zeng, W.; Yuan, H.; Liu, C.; Ren, Z.; Liu, C. Anal. Chem. 2020, 92, 10342. doi: 10.1021/acs.analchem.0c00390
7. [7]
  (7) Hsieh, C.-C.; Jiang, C.-M.; Chou, P.-T. Acc. Chem. Res. 2010, 43, 1364. doi: 10.1021/ar1000499
8. [8]
  (8) Demchenko, A. P.; Tang, K.-C.; Chou, P.-T. Chem. Soc. Rev. 2013, 42, 1379. doi: 10.1039/c2cs35195a
9. [9]
  (9) Tomin, V. I.; Demchenko, A. P.; Chou, P.-T. J. Photochem. Photobiol. C 2015,22, 1. doi: 10.1016/j.jphotochemrev.2014.09.005
10. [10]
  (10) Swinney, T. C.; Kelley, D. F. J. Chem. Phys. 1993, 99, 211. doi: 10.1063/1.465799
11. [11]
  (11) Chou, P.-T.; Martinez, M. L.; Clements, J. H. J. Phys. Chem. 1993, 97, 2618. doi: 10.1021/j100113a024
12. [12]
  (12) Shynkar, V. V.; Mély, Y.; Duportail, G.; Piémont, E.; Kiymchenko, A. S.; Demchenko, A. P. J. Phys. Chem. A 2003, 107, 9522. doi: 10.1021/jp035855n
13. [13]
  (13) Roshal, A. D.; Organero, J. A.; Douhal, A. Chem. Phys. Lett. 2003,379, 53. doi: 10.1016/j.cplett.2003.08.008
14. [14]
  (14) Douhal, A.; Sanz, M.; Carranza, M. A.; Organero, J. A.; Santos, L. Chem. Phys. Lett. 2004,394, 54. doi: 10.1016/j.cplett.2004.06.112
15. [15]
  (15) Chou, P.-T.; Pu, S.-C.; Cheng, Y.-M.; Yu, W.-S.; Yu, Y.-C.; Hung, F.-T. Hu, W.-P. J. Phys. Chem. A 2005, 109, 3777. doi: 10.1021/jp044205w
16. [16]
  (16) Rumble, C. A.; Breffke, J.; Maroncelli, M. J. Phys. Chem. B 2017, 121, 630. doi: 10.1021/acs.jpcb.6b12146
17. [17]
  (17) Ghosh, D.; Batuta, S.; Das, S.; Begum, N. A.; Mandal, D. J. Phys. Chem. B 2015,119, 5650. doi: 10.1021/acs.jpcb.5b00021
18. [18]
  (18) Ghosh, D.; Batuta, S.; Begum, N. A.; Mandal, D. Photochem. Photobiol. Sci. 2016,15, 266. doi: 10.1039/c5pp00377f
19. [19]
  (19) Chen, Y.; Yang, Y.; Zhao, Y.; Liu, S.; Li, Y. Phys. Chem. Chem. Phys. 2019,21, 17711. doi: 10.1039/c9cp03752g
20. [20]
  (20) Russo, M.; Štacko, P.; Nachtigallová, D.; Klάn, P. J. Org. Chem. 2020, 85, 3527. doi: 10.1021/acs.joc.9b03248
21. [21]
  (21) Lazarus, L. S.; Benninghoff, A. D.; Berreau, L. M. Acc. Chem. Res. 2020, 53, 2273. doi: 10.1021/acs.accounts.0c00402
22. [22]
  (22) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; et al. Gaussian 16, Revision A.03; Gaussian, Inc.: Wallingford CT, USA, 2016.
23. [23]
  (23) Zhao, C.-C.; Jiang, Y.-L.; Gao, R.-Y.; Yao, H.-D.; Wang, P.; Zhang, J.-P. Chem. Phys. Lett. 2021, 774, 138616. doi: 10.1016/j.cplett.2021.138616
24. [24]
  (24) Tseng, H.-W.; Liu, J.-Q.; Chen, Y.-A.; Chao, C.-M.; Liu, K.-M.; Chen, C.-L.; Lin, T.-C.; Hung, C.-H.; Chou, Y.-L.; Lin, T.-C.; et al. J. Phys. Chem. Lett. 2015,6, 1477. doi: 10.1021/acs.jpclett.5b00423
25. [25]
  (25) Tang, K.-C.; Chang M.-J.; Lin T.-Y.; Pan, H.-A.; Fang, T.-C.; Chen, K.-Y.; Hung, W.-Y.; Hsu, Y.-H.; Chou, P.-T. J. Am. Chem. Soc. 2011, 133, 17738. doi: 10.1021/ja2062693
26. [26]
  (26) Hirshfeld, F. L. Theor. Chim. Acta. 1977, 44, 129. doi: 10.1007/BF00549096
1. [1]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
3. [3]
  Yaling Chen . Basic Theory and Competitive Exam Analysis of Dynamic Isotope Effect. University Chemistry, 2024, 39(8): 403-410. doi: 10.3866/PKU.DXHX202311093
4. [4]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
5. [5]
  Shule Liu . Application of SPC/E Water Model in Molecular Dynamics Teaching Experiments. University Chemistry, 2024, 39(4): 338-342. doi: 10.3866/PKU.DXHX202310029
6. [6]
  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
7. [7]
  Yiying Yang , Dongju Zhang . Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction. University Chemistry, 2024, 39(3): 327-335. doi: 10.3866/PKU.DXHX202309074
8. [8]
  Jiajie Cai , Chang Cheng , Bowen Liu , Jianjun Zhang , Chuanjia Jiang , Bei Cheng . CdS/DBTSO-BDTO S型异质结光催化制氢及其电荷转移动力学. Acta Physico-Chimica Sinica, 2025, 41(8): 100084-. doi: 10.1016/j.actphy.2025.100084
9. [9]
  Shanghua Li , Malin Li , Xiwen Chi , Xin Yin , Zhaodi Luo , Jihong Yu . 基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑. Acta Physico-Chimica Sinica, 2025, 41(1): 2309003-. doi: 10.3866/PKU.WHXB202309003
10. [10]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
11. [11]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . ZnO/D-A共轭聚合物S型异质结高效光催化产H₂O₂及其电荷转移动力学研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-. doi: 10.3866/PKU.WHXB202406027
12. [12]
  Kexin Dong , Chuqi Shen , Ruyu Yan , Yanping Liu , Chunqiang Zhuang , Shijie Li . Integration of Plasmonic Effect and S-Scheme Heterojunction into Ag/Ag₃PO₄/C₃N₅ Photocatalyst for Boosted Photocatalytic Levofloxacin Degradation. Acta Physico-Chimica Sinica, 2024, 40(10): 2310013-. doi: 10.3866/PKU.WHXB202310013
13. [13]
  Yue Wu , Jun Li , Bo Zhang , Yan Yang , Haibo Li , Xian-Xi Zhang . Research on Kinetic and Thermodynamic Transformations of Organic-Inorganic Hybrid Materials for Fluorescent Anti-Counterfeiting Application information: Introducing a Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(6): 390-399. doi: 10.3866/PKU.DXHX202403028
14. [14]
  Lirui Shen , Kun Liu , Ying Yang , Dongwan Li , Wengui Chang . Synthesis and Application of Decanedioic Acid-N-Hydroxysuccinimide Ester: Exploration of Teaching Reform in Comprehensive Applied Chemistry Experiment. University Chemistry, 2024, 39(8): 212-220. doi: 10.3866/PKU.DXHX202312035
15. [15]
  Jiayu Gu , Siqi Wang , Jun Ling . Kinetics of Living Copolymerization: A Brief Discussion. University Chemistry, 2025, 40(4): 100-107. doi: 10.12461/PKU.DXHX202406012
16. [16]
  Guoqiang Chen , Zixuan Zheng , Wei Zhong , Guohong Wang , Xinhe Wu . 熔融中间体运输导向合成富氨基g-C₃N₄纳米片用于高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406021-. doi: 10.3866/PKU.WHXB202406021
17. [17]
  Hong-Tao Ji , Yu-Han Lu , Yan-Ting Liu , Yu-Lin Huang , Jiang-Feng Tian , Feng Liu , Yan-Yan Zeng , Hai-Yan Yang , Yong-Hong Zhang , Wei-Min He . Nd@C₃N₄-photoredox/chlorine dual catalyzed synthesis and evaluation of antitumor activities of 4-alkylated sulfonyl ketimines. Chinese Chemical Letters, 2025, 36(2): 110568-. doi: 10.1016/j.cclet.2024.110568
18. [18]
  Kai Han , Guohui Dong , Ishaaq Saeed , Tingting Dong , Chenyang Xiao . Morphology and photocatalytic tetracycline degradation of g-C3N4 optimized by the coal gangue. Chinese Journal of Structural Chemistry, 2024, 43(2): 100208-100208. doi: 10.1016/j.cjsc.2023.100208
19. [19]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-. doi: 10.3866/PKU.WHXB202408005
20. [20]
  Liang Ma , Zhou Li , Zhiqiang Jiang , Xiaofeng Wu , Shixin Chang , Sónia A. C. Carabineiro , Kangle Lv . Effect of precursors on the structure and photocatalytic performance of g-C3N4 for NO oxidation and CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100416-100416. doi: 10.1016/j.cjsc.2024.100416

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(176)
HTML views(21)

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