A strategy of chiral cation coordination to achieve a large luminescence dissymmetry factor in 1D hybrid manganese halides

一种利用手性阳离子配位策略在1D杂化锰卤化物中实现大发光不对称因子的方法

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Abstract

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 R/S-DACAMnBr(3), featuring a one-dimensional chain structure alternately coordinated by organic cations via edge-sharing MnOBr(5) 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(2+) centers to achieve intense orange CPL at 626 nm, yielding a remarkable luminescence dissymmetry factor (g (lum)) of 0.292 for S-DACAMnBr(3), 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 g (lum) 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 S-DACAMnBr(3)-based circularly polarized light-emitting diodes exhibiting a strong CPL signal at 620 nm with a g (lum) of 6.4 × 10(-3), alongside single-crystal photodetectors achieving a switching ratio of 7.72. These findings contribute valuable insights for amplifying the chiroptical activity of hybrid OIMHs via a strategy of chiral cation coordination, which may pave the way for the development of effective CPL materials toward diverse applications in the future.

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