Li Zenghui, Liu Xiaoyang, Bao Qidi, Wang Jing, Liu Xu, Gong Honghong, Han Tian, Feng Chao, Lu Dongmei, Yue Ling, Wu Chao, He Gang, Su Yuanting, Rao Bin
School of Chemistry, Xi'an Jiaotong University, Engineering Research Center of Energy Storage Materials and Devices, Ministry of Education, Xi'an 710049, China.
Frontier Institute of Science and Technology, Xi'an Jiaotong University, Xi'an 710049, China.
J Am Chem Soc. 2025 Jan 15;147(2):1452-1457. doi: 10.1021/jacs.4c16614. Epub 2024 Dec 31.
Herein, SUMO-LUMO inversion (SLI) radicals - were designed by the combination of the tris(2,4,6-trichlorophenyl)methyl (TTM) radical and pyridinium derivatives (electron-withdrawing groups) for the first time. The energy of the LUMO lies below that of the SUMO, which deviated from the Aufbau principle as an alternative electronic configuration beyond the well-established SOMO-HOMO inversed system. Thus, for SLI radicals, the injection of one extra electron preferred to occupy the LUMO rather than the SUMO, giving diradicals, one of which had been fully confirmed by single crystal analysis, VT-NMR and VT-EPR experiments, as well as DFT calculations. Furthermore, SLI radicals - exhibit photoluminescent properties and good photostability under UV irradiation ( > 24 days for ). This finding would open up new exploration on SLI radicals and their potential applications as photoelectromagnetic material.
在此，首次通过三（2,4,6-三氯苯基）甲基（TTM）自由基与吡啶鎓衍生物（吸电子基团）的组合设计出了SUMO-LUMO反转（SLI）自由基。最低未占分子轨道（LUMO）的能量低于单占据分子轨道（SUMO）的能量，这偏离了构造原理，是一种超越已确立的单占据分子轨道-最高占据分子轨道（SOMO-HOMO）反转体系的替代电子构型。因此，对于SLI自由基，额外注入的一个电子更倾向于占据LUMO而非SUMO，从而产生双自由基，其中之一已通过单晶分析、变温核磁共振（VT-NMR）和变温电子顺磁共振（VT-EPR）实验以及密度泛函理论（DFT）计算得到充分证实。此外，SLI自由基在紫外光照射下表现出光致发光特性和良好的光稳定性（照射超过24天）。这一发现将为SLI自由基及其作为光电磁材料潜在应用的新探索开辟道路。
