Formation of Slipped Dimer in <scp>6‐Pentafluorophenyl</scp>‐substituted Olympicenyl Radical
作者:Qin Xiang、Yupeng Guo、Jinlian Hu、Zhaoyang Li、Zhe Sun
DOI:10.1002/cjoc.202300370
日期:2023.11.15
Introduction of substituents to organic radical is important to increase the stability and realize its applications as multifunctional materials. In this work, pentafluorophenyl group was introduced to 6-position of olympicenyl radical (OR) via a newly designed synthetic strategy to afford the fourth OR derivative, OR4. Due to the combined electro-withdrawing effect and steric hindrance of pentafluorophenyl
向有机自由基中引入取代基对于提高其稳定性并实现其作为多功能材料的应用具有重要意义。在这项工作中,通过新设计的合成策略,将五氟苯基引入到奥林基自由基(OR)的6位上,得到第四种OR衍生物OR4。由于五氟苯基的吸电效应和空间位阻的综合作用,OR4在结晶状态下是稳定且可分离的。在以CH·F相互作用为主的单晶结构中发现了滑移二聚体。SQUID测量揭示了滑动二聚体的单线态-三线态能隙为-0.47 kcal·mol -1 ,表明SOMO-SOMO相互作用较弱。此外,与 6-三异丙基甲硅烷基乙炔基保护的 OR 衍生物相比,五氟苯基的吸电效应导致OR4的氧化波正移(0.15 V)。