Crystalline Germanium-Dipyrromethene Radicals:from a Delocalized Neutral to a Localized Cation  

作　　者：Yuyang Dai Manling Bao Wenjuan Wang Zhuofeng Xie Chunmeng Liu Yuanting Su 

机构地区：[1]College of Chemistry,Chemical Engineering and Materials Science,School of Radiation Medicine and Protection,Soochow University,Suzhou,Jiangsu,215123 China [2]State Key Laboratory of Coordination Chemistry,Nanjing University,Nanjing,Jiangsu,210023 China

出　　处：《Chinese Journal of Chemistry》2022年第20期2387-2392,共6页中国化学（英文版）

基　　金：support from the National Natural Science Foundation of China(Grant 22001184,Y.S.,11904425,C.L.);the Natural Science Foundation of Jiangsu Province(Grant BK20200849,Y.S.);the Natural Science Foundation of Jiangsu Higher Education Institutions of China(Grant 20KJB150002,Y.S.);the Entrepreneurship and Innovation Talent Program of Jiangsu Province(Y.S.,JSSCBS20210664,C.L.).

摘　　要：Both dipyrromethene complexes and radicals of heavier main group elements have been of high interest.However,cationic germanium radicals and dipyrromethene-based radicals of heavier main group elements are still escaped to be isolated.Herein,we report the isolation and full characterization of a neutral Ge(I)-masked dipyrromethene-based radical 3 and the first cationic Ge(III)-centered radical 5^(·+)as stable crystalline solids.3 behaves as a germanium(I)radical in its reaction with diphenyl disulfide to form the Ge-S bond,although X-ray crystallographic,EPR spectroscopic,computational studies revealed that the unpaired electron of 3 is mainly delocalized over the C_(9)N_(2)Ge backbone and the allylic radical character is also significant in 3.In contrast to 3,the spin density of 5^(·+)is mainly localized at the Ge center with minor contribution from the dipyrromethene ligand.Moreover,reduction of 5^(·+)with potassium graphite quantitatively regenerates 5,illustrating a reversible one-electron redox pair.

关 键 词：RADICALS Main group element GERMANIUM Dipyrromethene X-ray diffraction 

分 类 号：O62[理学—有机化学]