Robust free-base and metalated corrole radicals with reduction-induced emission  

作　　者：Pengfei Li Chulin Qu Fan Wu Hu Gao Chengyan Zhao Yue Zhao Zhen Shen 

机构地区：[1]State Key Laboratory of Coordination Chemistry,Collaborative Innovation Center of Advanced Microstructures,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing 210023,China [2]School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China [3]College of Materials Science and Engineering,Nanjing Forestry University,Nanjing 210037,China

出　　处：《Chinese Chemical Letters》2025年第2期398-403,共6页中国化学快报(英文版)

基　　金：supported by the National Natural Science Foundation of China(Nos.22271140,22071103,and 22371118)。

摘　　要：Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task.Here we report the synthesis of a stable,free-base benzocorrole(BC)radical containing only two inner NH protons via a retro-Diels-Alder conversion.The radical character of BC was fully supported by crystallographic analysis,spectroscopic evidence,and theoretical calculations.This neutral radical ligand allowed easy insertion of Zn(Ⅱ),Ga(Ⅲ),and Pd(Ⅱ)ions to produce radical complexes.All these radicals exhibited luminescence-on responses under weak reducing atmosphere,corresponding to the conversion to their aromatic anions.The red fluorescence was observed for BC and its Zn(Ⅱ)and Ga(Ⅲ)complexes,and the near-infrared phosphorescence(>900 nm)was detected for Pd(Ⅱ)complex at room temperature.Furthermore,Ga(Ⅲ)corrole exhibited a variation in fluorescence in response to axial coordination.Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.

关 键 词：RADICALS PORPHYRINOIDS Macrocyclic ligands LUMINESCENCE Redox chemistry 

分 类 号：O641.4[理学—物理化学]