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外消旋配体在具有近100%量子产率和多刺激响应的红光发射金属卤化物中诱导形成的灯笼状结构。

Lantern-Shaped Structure Induced by Racemic Ligands in Red-Light-Emitting Metal Halide with Near 100 % Quantum Yield and Multiple-Stimulus Response.

作者信息

Wu Yuechuan, Wang Shuaiqi, Lin Zhibin, Kang Liwen, Wu Junyan, Chen Qiushui, Lin Zhenghuan

机构信息

Fujian Key Laboratory of Polymer Materials College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 350007, China.

College of Chemistry, Fuzhou University, Fuzhou, 350108, China.

出版信息

Angew Chem Int Ed Engl. 2025 Jan 21;64(4):e202416062. doi: 10.1002/anie.202416062. Epub 2024 Oct 29.

Abstract

Organic-inorganic metal halides (OIMHs) have become a research hotspot in recent years due to their excellent luminescent properties and tunable emission wavelengths. However, the development of efficient red-light-emitting OIMHs remains a significant challenge. This work reports three Mn-based OIMHs derived from 1-methyl-1,2,3,4-tetrahydroisoquinoline hydrobromide: racemic one (Rac-TBM) and chiral ones (R-TBM and S-TBM). As a result of the synergism of chiral organic ligands inducing a unique lantern-shaped hybrid structure containing both tetrahedra and octahedra, Rac-TBM exhibits red-light emission with near-unity luminescence quantum yield. In comparison, the chiral counterparts R/S-TBM display strong green emission and circularly polarized luminescence (CPL) with a g value up to ±2.5×10. Interestingly, a mixture of R- and S-TBM can transform into Rac-TBM, successfully achieving a sensitive and reversible switch between red light of octahedra and green light of tetrahedra under external stimuli. The outstanding luminescent properties allow Rac-TBM to be utilized not only for X-ray radioluminescence with a detection limit down to 46.29 nGys, but also for advanced information encryption systems to achieve leak-proof decryption.

摘要

近年来,有机-无机金属卤化物(OIMHs)因其优异的发光性能和可调节的发射波长而成为研究热点。然而,开发高效的发红光OIMHs仍然是一项重大挑战。这项工作报道了三种由1-甲基-1,2,3,4-四氢异喹啉氢溴酸盐衍生的锰基OIMHs:外消旋体(Rac-TBM)和手性异构体(R-TBM和S-TBM)。由于手性有机配体的协同作用诱导形成了一种独特的包含四面体和八面体的灯笼状杂化结构,Rac-TBM呈现出发光量子产率接近1的红光发射。相比之下,手性对应物R/S-TBM显示出强烈的绿色发射和圆偏振发光(CPL),g值高达±2.5×10。有趣的是,R-TBM和S-TBM的混合物可以转化为Rac-TBM,在外部刺激下成功实现了八面体红光和四面体绿光之间的灵敏且可逆的切换。出色的发光性能使Rac-TBM不仅可用于检测限低至46.29 nGys的X射线辐射发光,还可用于先进的信息加密系统以实现防泄漏解密。

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