Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.
Advanced Research Institute of Multidisciplinary Science, Schools of Chemistry and Chemical Engineering, School of Materials Science and Engineering, Beijing Institute of Technology (BIT), Beijing 100081, China.
Inorg Chem. 2023 Jun 19;62(24):9722-9731. doi: 10.1021/acs.inorgchem.3c00997. Epub 2023 Jun 7.
Organic-inorganic hybrid metal halides have attracted widespread attention due to their excellent tunability and versatility. Here, we have selected pyridinium derivatives with different substituent groups or substitution positions as the organic templating cations and obtained six 1D chain-like structures. They are divided into three types: type I (single chain), type II (double chain), and type III (triple chain), with tunable optical band gaps and emission properties. Among them, only (2,4-LD)PbBr (2,4-LD = 2,4-lutidine) shows an exciton-dependent emission phenomenon, ranging from strong yellow-white to weak red-white light. By comparing its photoluminescence spectrum with that of its bromate (2,4-LD)Br, it is found that the strong yellow-white emission at 534 nm mainly came from the organic component. Furthermore, through a comparison of the fluorescence spectra and lifetimes of (2,4-LD)PbBr and (2-MP)PbBr (2-MP = 2-methylpyridine) with similar structures at different temperatures, we confirm that the tunable emission of (2,4-LD)PbBr comes from different photoluminescent sources corresponding to organic cations and self-trapped excitons. Density functional theory calculations further reveal that (2,4-LD)PbBr has a stronger interaction between organic and inorganic components compared to (2-MP)PbBr. This work highlights the importance of organic templating cations in hybrid metal halides and the new functionalities associated with them.
有机-无机杂化金属卤化物由于其优异的可调谐性和多功能性而引起了广泛关注。在这里,我们选择了具有不同取代基或取代位置的吡啶鎓衍生物作为有机模板阳离子,并获得了六种 1D 链状结构。它们分为三种类型:I 型(单链)、II 型(双链)和 III 型(三链),具有可调谐的光学带隙和发射特性。其中,只有 (2,4-LD)PbBr(2,4-LD = 2,4- 二甲基吡啶)表现出激子依赖的发射现象,从强黄-白光到弱红-白光。通过将其光致发光光谱与其溴酸盐 (2,4-LD)Br 的光致发光光谱进行比较,发现 534nm 处的强黄-白光发射主要来自有机部分。此外,通过比较不同温度下具有相似结构的 (2,4-LD)PbBr 和 (2-MP)PbBr(2-MP = 2- 甲基吡啶)的荧光光谱和荧光寿命,我们证实了 (2,4-LD)PbBr 的可调发射来自于与有机阳离子和自陷激子对应的不同光致发光源。密度泛函理论计算进一步表明,与 (2-MP)PbBr 相比,(2,4-LD)PbBr 中有机和无机成分之间的相互作用更强。这项工作强调了有机模板阳离子在杂化金属卤化物中的重要性以及与之相关的新功能。