Jin Qianrong, Wu Rui, Pan Yuexiao, Ding Yihong, Lian Hongzhou, Lin Jun, Li Liyi
Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University Wenzhou 325035 P.R. China
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences Changchun 130022 P. R. China
Chem Sci. 2024 Sep 18;15(41):17173-82. doi: 10.1039/d4sc04706k.
The burgeoning demand for materials with tunable photoluminescence properties for applications has necessitated the exploration of novel luminescent materials. This study presents the synthesis and characterization of a novel 0D organic-inorganic hybrid metal halide (OIHMH) single crystal, CHNCdBr, which exhibits intriguing luminescent properties upon Mn doping. The introduction of single Mn ions results in a dual-emission, with the unexpected emergence of a red emission peak at 627 nm, in addition to the conventional tetrahedral green emission at 525 nm. This dual-emission is attributed to the distinct inter-tetrahedral distances within the crystal structure of CHNCdBr with varying distances between [CdBr] tetrahedra, influencing the spatial distribution and interaction of the [MnBr] tetrahedra. Electron paramagnetic resonance (EPR) spectroscopy and theoretical calculations reveal the 627 nm and 525 nm emissions are attributed to the d-d transition of magnetic coupled Mn-Mn pairs and isolated Mn ions, respectively. This study not only advances the understanding of the luminescence mechanisms of Mn but also paves the way for the development of tunable luminescent materials.
对具有可调光致发光特性的材料的需求不断增长，这就需要探索新型发光材料。本研究介绍了一种新型零维有机-无机杂化金属卤化物（OIHMH）单晶CHNCdBr的合成与表征，该单晶在锰掺杂后表现出有趣的发光特性。单个锰离子的引入导致了双重发射，除了在525 nm处的传统四面体绿色发射外，还意外地出现了一个在627 nm处的红色发射峰。这种双重发射归因于CHNCdBr晶体结构中不同[CdBr]四面体之间的四面体间距离不同，影响了[MnBr]四面体的空间分布和相互作用。电子顺磁共振（EPR）光谱和理论计算表明，627 nm和525 nm的发射分别归因于磁耦合锰-锰对和孤立锰离子的d-d跃迁。这项研究不仅增进了对锰发光机制的理解，也为可调谐发光材料的发展铺平了道路。
