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

doi:10.1007/s40242-022-2015-z

Chemical Research in Chinese Universities ›› 2022, Vol. 38 ›› Issue (3): 798-802.doi: 10.1007/s40242-022-2015-z

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

CHEN Zhangwu and LI Feng

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China

Received:2022-01-14 Revised:2022-02-12 Online:2022-06-01 Published:2022-02-17
Contact: LI Feng E-mail:lifeng01@jlu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (Nos.51925303 and 91833304) and the Programme for Jilin University Science and Technology Innovative Research Team(JLUSTIRT), China(No.2019TD-33).

Abstract

Abstract: 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.

Key words: Luminescent radical, Singly occupied molecular orbital (SOMO)-highest doubly occupied molecular orbital(HOMO) conversion, Non-Aufbau, Turn-on fluorescence

CHEN Zhangwu and LI Feng. Proton-induced Conversion from Non-Aufbau to Aufbau Electronic Structure of an Organic Radical with Turn-on Fluorescence[J]. Chemical Research in Chinese Universities, 2022, 38(3): 798-802.

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

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