Wang Fei, Li Xingjun, Chen Tianqi, Wang Liqing, Li Chenliang, Zhang Wei, Yuan Wen, Lu Shan, Li Lina, Chen Xueyuan
State Key Laboratory of Structural Chemistry, Fujian Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou Fujian 350002 China
College of Chemistry and Materials Science, Fujian Normal University Fuzhou Fujian 350117 China.
Chem Sci. 2025 May 14;16(24):11012-11020. doi: 10.1039/d5sc01615k. eCollection 2025 Jun 18.
Chiral organic-inorganic metal halides (OIMHs) have emerged as a new class of promising circularly polarized luminescence (CPL) materials owing to their structural tunability and fascinating optoelectronic properties. However, the development of high-performance chiral hybrid OIMHs remains a critical challenge, largely attributed to the absence of effective strategies for modulating chiroptical activity. Herein, we present enantiomeric hybrid manganese bromides, denoted as /-DACAMnBr, featuring a one-dimensional chain structure alternately coordinated by organic cations edge-sharing MnOBr octahedra, which establishes a robust chiral transfer pathway from organic cations to inorganic emissive centers. This structural design synergizes with the high intrinsic emission efficiency of Mn centers to achieve intense orange CPL at 626 nm, yielding a remarkable luminescence dissymmetry factor ( ) of 0.292 for -DACAMnBr, which surpasses most reported chiral OIHMs by 1-3 orders of magnitude. Remarkably, a positive magneto-chiroptical effect under a 1.6 T magnetic field amplifies the value to 0.321 at room temperature, demonstrating the first example of magnetic-field-enhanced CPL in lead-free OIMHs. The practical viability is further evidenced by -DACAMnBr-based circularly polarized light-emitting diodes exhibiting a strong CPL signal at 620 nm with a of 6.4 × 10, alongside single-crystal photodetectors achieving a switching ratio of 7.72. These findings contribute valuable insights for amplifying the chiroptical activity of hybrid OIMHs a strategy of chiral cation coordination, which may pave the way for the development of effective CPL materials toward diverse applications in the future.
手性有机-无机金属卤化物（OIMHs）因其结构可调性和迷人的光电特性，已成为一类有前途的圆偏振发光（CPL）材料。然而，高性能手性混合OIMHs的开发仍然是一项严峻挑战，这主要归因于缺乏调节手性光学活性的有效策略。在此，我们展示了对映体混合溴化锰，记为/-DACAMnBr，其具有由有机阳离子与边共享MnOBr八面体交替配位的一维链结构，这建立了从有机阳离子到无机发射中心的稳健手性转移途径。这种结构设计与Mn中心的高本征发射效率协同作用，在626nm处实现了强烈的橙色CPL，对于-DACAMnBr产生了显著的发光不对称因子（）0.292，比大多数报道的手性OIHMs高出1-3个数量级。值得注意的是，在1.6T磁场下的正磁圆二色效应在室温下将值放大到0.321，这证明了无铅OIMHs中磁场增强CPL的首个实例。基于-DACAMnBr的圆偏振发光二极管在620nm处表现出强CPL信号，为6.4×10，以及单晶光电探测器实现7.72的开关比，进一步证明了其实际可行性。这些发现为通过手性阳离子配位策略放大混合OIMHs的手性光学活性提供了有价值的见解，这可能为未来开发用于各种应用的有效CPL材料铺平道路。
