文献类型：期刊文献

英文题名：Highly Luminescent Chiral Double π-Helical Nanoribbons

作者：Liu, Yujian[1];Li, Zuoyu[1];Wang, Ming-Wei[1];Chan, Jiangtao[1];Liu, Guogang[2,3];Wang, Zhaohui[1];Jiang, Wei[1]

机构：[1]Tsinghua Univ, Dept Chem, Key Lab Organ Optoelect & Mol Engn, Beijing 100084, Peoples R China;[2]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn,Key Lab Adv Mat,Inst Fine Chem, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Inst Fine Chem,Joint Int Res Lab Precis Chem,Sch C, Shanghai 200237, Peoples R China

年份：2024

卷号：146

期号：8

起止页码：5295

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20240915640225);WOS:【SCI-EXPANDED(收录号:WOS:001166813700001)】；

基金：This work was financially supported by the National Natural Science Foundation of China (NSFC) (No. 22122503, 22235005, and 22275112). The authors acknowledge Dr. Zhen-Yi Zhang from Bruker (Beijing) Scientific Technology Co., Ltd. for helpful discussions on X-ray crystallography.

语种：英文

外文关键词：Density functional theory - Dimers - Luminescence - Nanoribbons - Stereochemistry

摘要：Unveiling the mechanism behind chirality propagation and dissymmetry amplification at the molecular level is of significance for the development of chiral systems with comprehensively outstanding chiroptical performances. Herein, we have presented a straightforward Cu-mediated Ullmann homocoupling approach to synthesize perylene diimide-entwined double pi-helical nanoribbons encompassing dimer, trimer, and tetramer while producing homochiral or heterochiral linking of chiral centers. A significant dissymmetry amplification was achieved, with absorption dissymmetry factors (|g abs|) increasing from 0.009 to 0.017 and further to 0.019, and luminescence dissymmetry factors (|g lum|) rising from 0.007 to 0.013 and eventually to 0.015 for homochiral double pi-helical oligomers. The disparity of magnetic transition dipole moment ( m ) densities in homochiral and heterochiral tetramers by time-dependent density functional theory calculations confirmed that homochiral oligomerization can maximize the total m , which is favorable for achieving ever-increasing g factors. Notably, these double pi-helices exhibited exceptional photoluminescence quantum yields (phi PL) ranging from 83 to 95%. The circularly polarized luminescence brightness (B CPL) eventually reached a remarkable 575 M-1 cm-1 for the homochiral tetramer, which is among the highest values reported for chiral small molecules. This kind of linearly extended double pi-helices offers a platform for a comprehensive understanding of the mechanism behind chirality propagation and dissymmetry amplification.