Ma Lishuang, Feng Wenxu, Xi Yanyan, Chen Xuebo, Lin Xufeng
College of Science, China University of Petroleum (East China), Qingdao 266580, People's Republic of China.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, P. R. China.
J Org Chem. 2022 Jan 21;87(2):944-951. doi: 10.1021/acs.joc.1c02005. Epub 2022 Jan 11.
Electron donor-acceptor (EDA) complex photochemistry has become a burgeoning topic in the synthetic radical chemistry mediated by visible light; however, the theoretical insights into the reaction mechanisms are limited. Herein, accurate electronic structure calculations at the CASPT2//CASSCF/PCM level of theory were performed to investigate the paradigm example of EDA complex-enabled photoreaction for visible-light-driven dearomative perfluoroalkylation of β-naphthol. The excitation energy levels of the EDA complex are controlled by noncovalent interactions because the photoinduced intermolecular charge is enhanced when the noncovalent interaction becomes weaker, leading to the broad spectra ranging from UVA (<380 nm) to visible light (>500 nm). The competitiveness of the radical-radical coupling over the radical chain pathway is also regulated due to the tunable radical concentrations varying the excitation wavelength.
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新兴的课题；然而，对其反应机理的理论认识有限。在此，我们在CASPT2//CASSCF/PCM理论水平上进行了精确的电子结构计算，以研究基于EDA络合物的光反应这一范例，即β-萘酚的可见光驱动去芳构化全氟烷基化反应。EDA络合物的激发能级由非共价相互作用控制，因为当非共价相互作用变弱时，光诱导的分子间电荷增强，导致光谱范围从紫外光A（<380 nm）扩展到可见光（>500 nm）。由于激发波长改变会使自由基浓度可调，自由基-自由基偶联相对于自由基链途径的竞争力也受到调控。
