文献类型：期刊文献

英文题名：Stepwise Modification of Carborane-Fused Heterocycles for Enhanced Circularly Polarized Luminescence

作者：Dong, Beibei[1];Wang, Weixian[2,3];Wang, Puzhao[1];Zhu, Rongji[4];Feng, Ting[1];Zou, Chao[2,5];Mu, Xin[1]

机构：[1]East China Univ Sci & Technol, Engn Res Ctr Pharmaceut Proc Chem, Sch Pharm, Minist Educ, Shanghai, Peoples R China;[2]Songshan Lake Mat Lab, Frontier Res Ctr, Funct Coordinat Mat Grp, Dongguan, Peoples R China;[3]Yunnan Minzu Univ, Sch Chem & Environm, Key Lab Green Chem Mat Univ Yunnan Prov, Kunming, Peoples R China;[4]Southern Univ Sci & Technol, Dept Chem, Shenzhen, Peoples R China;[5]Chinese Acad Sci, Dongguan Inst Mat Sci & Technol, Guangzhou, Guangdong, Peoples R China

年份：2026

外文期刊名：ADVANCED OPTICAL MATERIALS

收录：;EI(收录号：20263021159841);Scopus(收录号：2-s2.0-105045354425);WOS:【SCI-EXPANDED(收录号:WOS:001827726000001)】；

基金：X.M. is grateful for financial support from the Open Research Fund of Songshan Lake Materials Laboratory (2023SLABFN12), the Natural Science Foundation of Shanghai (22ZR1416700), and the Engineering Research Center of Pharmaceutical Process Chemistry, Ministry of Education. C.Z. is thankful for the start-up funding from Songshan Lake Materials Laboratory (Y1D1061C11). W.W. thanks the supports from Guangdong Basic and Applied Basic Research Foundation (2023A1515110773) and Yunnan Key Laboratory of Chiral Functional Substance Research and Application (202402AN360010). The authors are grateful for computational support from the CHEM-HPC cluster (Department of Chemistry, SUSTech) and the high-performance computing facilities of the Center for Computational Science and Engineering at Southern University of Science and Technology. The authors are grateful for instrumental support from the Research Center of Analysis and Test, East China University of Science and Technology.

语种：英文

外文关键词：B-N Bond Formation; carborane; circularly polarized luminescence; heterocycle; phosphorescence

摘要：Herein, we report the design and synthesis of m-carborane-based chiral luminescent molecules with significantly improved chiroptical properties. These structurally unique molecules are constructed via a stepwise functionalization strategy. This includes an initial double B-N cross-coupling with atropisomeric 1,1'-binaphthyl-2,2'-diamine (BINAM) scaffolds to form a m-carborane-fused eight-membered heterocycle. Next, arylation occurs at spatially congested N-H sites, followed by final gold(I) complexation. Experimental and theoretical investigations show that this design systematically rigidifies the framework, which is demonstrated by comparing changes in the binaphthyl dihedral angles between the ground (S0) and excited (S1) states. Amplification of the photoluminescence dissymmetry factor (|glum|) from approximately 1.5 & times; 10-3 to as high as 1.1 & times; 10-2, a record for carborane-containing chiroptical small molecules in fluidic solution, has also been achieved. The circularly polarized luminescence (CPL) signals of these molecules challenge the established paradigm linking CPL signs to dihedral angles, highlighting the unique influence of the m-carborane core. Additionally, doping a small amount of the heterocycle-gold(I) complex into a gold(I) chloride matrix result in a long-persistent afterglow lasting up to four seconds.