School of Materials Science and Engineering, Smart Sensing Interdisciplinary Science Center, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tongyan Road 38, Tianjin 300350, P. R. China.
Mater Horiz. 2023 Mar 6;10(3):1005-1011. doi: 10.1039/d2mh01429g.
The striking chemical variability of hybrid organic-inorganic metal halides (HOMHs) endows them with fascinating optoelectronic properties. The inorganic skeletons of HOMHs are often flexible and their lattice deformations could serve as an effective factor for enabling the functionalities of HOMHs. Here, the linear and nonlinear optical properties of zero-dimensional (0D) tin(IV) halides have been tuned by structural distortion facilitated by the chiral amines. Enantiopure -methylbenzyl ammoniums (XMBA, X = Cl, F) effectively transfer their chirality to the inorganic scaffolds when forming the tin(IV) halides, which enables polar arrangements in their crystals and leads to outstanding second-order nonlinear optical performances. In contrast, the racemic mixture of - and -FMBA results in the formation of HOMHs with room temperature phosphorescence. The lower lattice deformation in (-FMBA)SnCl restrains the non-radiative decay from electron-phonon coupling and facilitates the photoluminescence. Meanwhile, the marked π-π interaction stabilizes the T state for phosphorescent emission. These distinct linear and nonlinear optical properties denote the important role that the lattice distortion plays in tuning the optical properties of low-dimensional HOMHs, and offer a promising perspective of 0D tin(IV) halides for applications in optoelectronic materials and devices.
杂化有机-无机金属卤化物（HOMHs）显著的化学多变性赋予了它们迷人的光电性能。HOMHs 的无机骨架通常具有柔性，其晶格变形可以作为实现 HOMHs 功能的有效因素。在这里，通过手性胺促进的结构变形来调整零维（0D）锡（IV）卤化物的线性和非线性光学性质。当形成锡（IV）卤化物时，手性的 -甲基苄基氨（XMBA，X = Cl，F）有效地将其手性传递给无机支架，这使得它们的晶体中产生了极性排列，从而导致了出色的二阶非线性光学性能。相比之下，-和 -FMBA 的外消旋混合物导致室温磷光 HOMHs 的形成。（-FMBA）SnCl 中较低的晶格变形限制了电子-声子耦合的非辐射衰减，并促进了光致发光。同时，明显的 π-π 相互作用稳定了 T 态磷光发射。这些明显的线性和非线性光学性质表明，晶格变形在调整低维 HOMHs 的光学性质方面起着重要作用，并为 0D 锡（IV）卤化物在光电材料和器件中的应用提供了有前景的视角。
