Proton-induced Conversion from Non-Aufbau to Aufbau Electronic Structure of an Organic Radical with Turn-on Fluorescence  

作　　者：CHEN Zhangwu LI Feng 

机构地区：[1]State Key Laboratory of Supramolecular Structure and Materials,College of Chemistry,Jilin University,Changchun,130012,P.R.China

出　　处：《Chemical Research in Chinese Universities》2022年第3期798-802,共5页高等学校化学研究（英文版）

基　　金：This work was supported by the National Natural Science Foundation of China(Nos.51925303 and 91833304);the Programme for Jilin University Science and Technology Innovative Research Team(JLUSTIRT),China(No.2019TD-33).

摘　　要：We report a donor-acceptor(D-A)type non-luminescent neutral radical,tris-2,4,6-trichlorophenylmethyl-N,N-dimethyl-9H-carbazol-3-amine(TTM-Cz-DMA).The results of cyclic voltammetry and quantum chemistry calculation confirm TTM-Cz-DMA has the non-Aufbau electronic structure,which means the singly occupied molecular orbital(SOMO)lies below the highest doubly occupied molecular orbital(HOMO).The non-Aufbau electronic structure changes to the Aufbau electronic structure after protonation and exhibits proton-responsive turn-on fluorescence,which is totally reversible by deprotonation.The dihedral angle between donor and acceptor moieties of TTM-Cz-DMA in excited state reduces from 88°to 62°after protonation,causing the turn-on fluorescence.Our results offer a viewing angle to understand the luminescence of radicals and provide a possible application of proton detection.

关 键 词：Luminescent radical Singly occupied molecular orbital(SOMO)-highest doubly occupied molecular orbital(HOMO)conversion Non-Aufbau Turn-on fluorescence 

分 类 号：O62[理学—有机化学]