Li Jing, Luo Qiulian, Wei Jianwu, Zhou Liya, Chen Peican, Luo Binbin, Chen Yibo, Pang Qi, Zhang Jin Zhong
School of Chemistry and Chemical Engineering/State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures/Guangxi Key Laboratory of Electrochemical Energy Materials/Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University, Nanning, 530004, Guangxi, P. R. China.
Department of Chemistry and Chemical Engineering, Shantou University, Shantou, 515063, Guangdong, P. R. China.
Angew Chem Int Ed Engl. 2024 Jun 10;63(24):e202405310. doi: 10.1002/anie.202405310. Epub 2024 May 7.
Chiral hybrid metal halides hold great potential as circularly polarized luminescence light sources. Herein, we have obtained two enantiomeric pairs of one-dimensional hybrid chiral manganese(II) chloride single crystals, R/S-(3-methyl piperidine)MnCl (R/S-1) and R/S-(3-hydroxy piperidine)MnCl (R/S-2), crystallizing in the non-centrosymmetric space group P222. In comparison to R/S-1, R/S-2 single crystals not only show red emission with near-unity photoluminescence quantum yield (PLQY) and high resistance to thermal quenching but also exhibit circularly polarized luminescence with an asymmetry factor (g) of 2.5×10, which can be attributed to the enhanced crystal rigidity resulting from the hydrogen bonding networks between R/S-(3-hydroxy piperidine) cations and [MnCl] chains. The circularly polarized luminescence activities originate from the asymmetric [MnCl] luminophores induced by N-H⋅⋅⋅Cl hydrogen bonding with R/S-(3-hydroxy piperidine). Moreover, these samples demonstrate great application potential in circularly polarized light-emitting diodes and X-ray scintillators. This work shows a highly efficient photoluminescent Mn-based halide and offers a strategy for designing multifunctional chiral metal halides.
手性杂化金属卤化物作为圆偏振发光光源具有巨大潜力。在此，我们获得了两对对映体的一维杂化手性氯化锰（II）单晶，即R/S-(3-甲基哌啶)MnCl（R/S-1）和R/S-(3-羟基哌啶)MnCl（R/S-2），它们结晶于非中心对称空间群P222。与R/S-1相比，R/S-2单晶不仅呈现出具有近单位光致发光量子产率（PLQY）的红色发射以及对热猝灭的高抗性，还展现出不对称因子（g）为2.5×10的圆偏振发光，这可归因于R/S-(3-羟基哌啶)阳离子与[MnCl]链之间的氢键网络导致的晶体刚性增强。圆偏振发光活性源于由N-H⋅⋅⋅Cl氢键与R/S-(3-羟基哌啶)诱导的不对称[MnCl]发光体。此外，这些样品在圆偏振发光二极管和X射线闪烁体中展现出巨大的应用潜力。这项工作展示了一种高效的基于锰的光致发光卤化物，并为设计多功能手性金属卤化物提供了一种策略。
