Ma Lishuang, Li Jianhao, Zhang Xiaorui, Yang Yanting, Lin Xufeng, Chen Xuebo
College of Chemistry and Chemical Engineering, State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, P. R. China.
Key Laboratory of Theoretical and Computational Photochemistry of Ministry of Education, Department of Chemistry, Beijing Normal University, Beijing 100875, P. R. China.
J Phys Chem Lett. 2024 Mar 28;15(12):3412-3418. doi: 10.1021/acs.jpclett.4c00455. Epub 2024 Mar 19.
Electron donor-acceptor (EDA) complex photochemistry has emerged as a vibrant area in visible-light-mediated synthetic radical chemistry. However, theoretical insights into the reaction mechanisms remain limited. Our study investigates the influence of solvent polarity and halogen atom types on radical reaction pathways in EDA complexes. We demonstrate that solvent polarity modulates the charge transfer and spatial arrangement within EDA complexes, thereby influencing their stability and reaction kinetics. Iodide ions play a crucial role in facilitating free radical generation and stabilizing reaction intermediates. Different halogen atom types exhibit distinct effects on radical reactions. Variations in radical concentration and solvent environment further affect the pathway selectivity. Additionally, light conditions influence the free radical generation and pathway selectivity. Our findings enhance the understanding of EDA complex photochemistry and radical reactions, offering insights for organic synthesis and photochemistry applications.
电子供体-受体（EDA）络合物光化学已成为可见光介导的合成自由基化学中一个充满活力的领域。然而，对其反应机理的理论认识仍然有限。我们的研究考察了溶剂极性和卤素原子类型对EDA络合物中自由基反应途径的影响。我们证明，溶剂极性调节EDA络合物内的电荷转移和空间排列，从而影响其稳定性和反应动力学。碘离子在促进自由基生成和稳定反应中间体方面起着关键作用。不同的卤素原子类型对自由基反应表现出不同的影响。自由基浓度和溶剂环境的变化进一步影响途径选择性。此外，光照条件影响自由基的生成和途径选择性。我们的研究结果加深了对EDA络合物光化学和自由基反应的理解，并为有机合成和光化学应用提供了见解。
