Eco-friendly organic–inorganic hybrid metal halides (OIMHs) are widely recognized as promising candidates for next-generation semiconductor materials. However, achieving inherent moisture stability in OIMHs remains a significant challenge due to the highly hygroscopic nature of the halide structures. In response, a strategy to precisely modify the organic cation (18-ACE: 4,13-diaza-18-crown 6-ether) was developed by introducing hydrophobic benzyl groups into 18-ACE, forming a protective layer that enhances the moisture stability of the OIMHs. Specifically, benzyl groups were incorporated into 18-ACE to create 18-ACE-Bn, which was then used as an organic component to construct zero-dimensional Mn-based (18-ACE)MnBr₄ and (18-ACE-Bn)MnBr₄·H₂O, exhibiting photoluminescence quantum yields (PLQYs) of 68.18% and 97.17%, respectively. Notably, (18-ACE-Bn)MnBr₄·H₂O demonstrates exceptional moisture stability compared to (18-ACE)MnBr₄, retaining 97% of its initial PLQY even after 180 days of exposure to 70% relative humidity. Molecular dynamics and density functional theory calculations indicate that this superior stability is attributed to the terminal benzyl groups embedded within the inorganic framework, forming a compact structure with abundant weak interactions. Leveraging the unique spectral characteristics of (18-ACE-Bn)MnBr₄·H₂O, a high-performance WLED with a wide color gamut of 125.2% NTSC (National Television Standard Committee) was developed, highlighting its potential for backlight display applications.

中文翻译：

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有机阳离子的精确改性，以提高 Mn 基卤化物的水分稳定性和发光效率


环保的有机-无机杂化金属卤化物 （OIMH） 被广泛认为是下一代半导体材料的有前途的候选材料。然而，由于卤化物结构的高度吸湿性，在 OIM 中实现固有的水分稳定性仍然是一项重大挑战。作为回应，通过将疏水性苄基引入 18-ACE 中，开发了一种精确修饰有机阳离子（18-ACE：4,13-二氮杂-18-冠 6-醚）的策略，形成增强 OIMH 水分稳定性的保护层。具体来说，将苄基掺入 18-ACE 中生成 18-ACE-Bn，然后将其用作有机组分构建零维 Mn 基 （18-ACE）MnBr₄ 和 （18-ACE-Bn）MnBr₄·H₂O，光致发光量子产率 （PLQY） 分别为 68.18% 和 97.17%。值得注意的是，（18-ACE-Bn）MnBr₄·与 （18-ACE）MnBr₄ 相比，H₂O 表现出卓越的水分稳定性，即使在 70% 相对湿度下暴露 180 天后，仍能保持 97% 的初始 PLQY。分子动力学和密度泛函理论计算表明，这种卓越的稳定性归因于嵌入无机框架内的末端苄基，形成具有丰富弱相互作用的致密结构。利用 （18-ACE-Bn）MnBr₄·H₂O 是一款高性能 WLED，具有 125.2% NTSC（美国国家电视标准委员会）的宽色域，凸显了其在背光显示应用方面的潜力。