Symmetry-Broken Intermolecular Charge Separation of Cationic Radicals

文献类型： 外文期刊

第一作者： Liu, Guanghua

作者： Liu, Guanghua;Gao, Lei;Xiao, Yao;Du, Bochao;Gong, Jianye;Meng, He;Wang, Jianguo;Wang, Qing;Han, Yi;Chi, Chunyan;Dai, Gaole;Hu, Jinlian;Sun, Zhe;Zhang, Fujin;Li, Xiang;Li, Xiang;Shi, Xueliang

作者机构：

关键词： Cationic Radical; Mixed Valence Complex; Nitrogen Doping; Quadrupole; Symmetry Broken Charge Separation

期刊名称：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION （ 影响因子：16.6； 五年影响因子：15.3 ）

ISSN： 1433-7851

年卷期： 2023 年

页码：

收录情况： SCI

摘要： A quadrupolar compound Pyr-BA with two pyrrole-type nitrogen atoms doped externally was prepared in this work. In high contrast with other pi ionic radicals, its cationic radical Pyr-BA center dot(+) undergoes unusual symmetry-broken charge separation (SB-CS), generating the mixed valence complex of Pyr-BA(+1-q)center dot center dot center dot Pyr-BA(+1+q), where q is the degree of charge transfer. Variable-temperature (VT) single-crystal analysis, absorption and EPR experiments all confirmed that aggregation and lower temperature would help to facilitate this SB-CS process. Gibbs energy calculations and gauge-including magnetically induced current simulation both validate that, for Pyr-BA center dot(+), SB-CS behavior is more favorable than the conventional dimerization mode. To the best of our knowledge, this is the first study that shows solid single-crystal evidence for spontaneous SB-CS between identical ionic radicals. Such a unique phenomenon is of great significance both in terms of fundamental aspects and uncharted material science.

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