文献类型：期刊文献

英文题名：Isoelectronic Substitution-Induced Intrachromophoric SymmetryBreaking Charge Separation

作者：Hu, Shunlong[1];Hu, Ke[2];Jin, Xin[1];Liu, Guogang[1];Liu, Yujian[3];Wang, Zhaolong[4];Chen, Kai[1];Zhao, Chengxi[1];Zhang, Zhiyun[1];Qu, Da-Hui[1];Chen, Jinquan[2];Jiang, Wei[1,3];Wang, Zhaohui[1,3,5]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat & Joint Int Res Lab Precis Chem &, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[2]East China Normal Univ, State Key Lab Precis Spect, Shanghai 200241, Peoples R China;[3]Tsinghua Univ, Dept Chem, Key Lab Organ Optoelect & Mol Engn, Beijing, Peoples R China;[4]Chinese Acad Sci, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China;[5]Chinese Acad Sci, Dalian Inst Chem Phys, Collaborat Innovat Ctr Chem Energy Mat iChEM, Dalian 116023, Peoples R China

年份：2025

卷号：7

期号：10

起止页码：3107

外文期刊名：CCS CHEMISTRY

收录：WOS:【ESCI(收录号:WOS:001402253600001)】；

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

语种：英文

外文关键词：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 the pi-pi stacking 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.