文献类型：期刊文献

中文题名：Isoelectronic Substitution-Induced Intrachromophoric Symmetry-Breaking Charge Separation

作者：Shunlong Hu[1];Ke Hu[2];Xin Jin[1];Guogang Liu[1];Yujian Liu[3];Zhaolong Wang[4];Kai Chen[1];Chengxi Zhao[1];Zhiyun Zhang[1];Da-Hui Qu[1];Jinquan Chen[2];Wei Jiang[1,3];Zhaohui Wang[1,3]

机构：[1]Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering,Feringa Nobel Prize Scientist Joint Research Center,Frontiers Science Center for Materiobiology and Dynamic Chemistry,Institute of Fine Chemicals,School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237;[2]State Key Laboratory of Precision Spectroscopy,East China Normal University,Shanghai 200241;[3]Key Laboratory of Organic Optoelectronics and Molecular Engineering,Department of Chemistry,Tsinghua University,Beijing 100084;[4]State Key Laboratory of Molecular Reaction Dynamics and Collaborative Innovation Center of Chemistry for Energy Materials(iChEM),Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023

年份：2025

卷号：7

期号：10

起止页码：3107

中文期刊名：CCS Chemistry

外文期刊名：中国化学会会刊(英文)

基金：financially supported by the National Natural Science Foundation of China(grant nos.22235005,22122503,22461160284,22401094,92156024,and 92356307);the Natural Science Foundation of Shanghai(grant no.24ZR1416100).

语种：英文

中文关键词：charge transfer;symmetry-breaking charge separation;rylene diimides;aromaticity reversal;pseudo Jahn-Teller effect

摘要：Symmetry-breaking charge separation(SB-CS)originating from natural photosynthesis is important for improving the efficiency of energy conversion from solar to electrical or chemical energy.However,SB-CS commonly occurs between two or more identical chromophores and is highly sensitive to theπ–πstacking or bridging modes,posing significant challenges for their applications.In this study,we demonstrate that SB-CS can occur within a single chromophore by replacing a specific naphthalene unit with an isoelectronic 10,9-borazaronaphthalene unit.Unlike the mechanisms of interchromophoric SB-CS dominated by electronic coupling,intrachromophoric SB-CS is realized by aromaticity reversal and the pseudo Jahn–Teller effect.Distinctive mechanisms endow intrachromophoric SB-CS with unique properties,such as broad absorption,tolerance to different chromophores,and distinctive dependence on solvent dielectric constants.Most surprisingly,the time-resolved circular dichroism spectra revealed that intrachromophoric SB-CS is accompanied by symmetry breaking of the chirality of the chromophore.These findings provide a new perspective on the development of SB-CS systems and their applications in optoelectronic and photochemical devices.