Sun Xiao, Li Yuting, Qiu Xinyu, Zhou Xuanshan, Mao Yangxue, Chen Guoyong, Zhou Lin, Guo Wenjing, Wei Zhenhong, Cai Hu
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang City 330031, PR China.
ACS Appl Mater Interfaces. 2025 Feb 19;17(7):10845-10852. doi: 10.1021/acsami.4c21385. Epub 2025 Feb 6.
Organic-inorganic hybrid chiral small-molecule materials combine the inherent properties of both components; however, studies integrating chirality with rare-earth double-perovskite materials are limited. In this work, we synthesized two enantiomers of three-dimensional (3D) hybrid rare-earth double-perovskites, [-3-HDMP]CsEu(NO) () and [-3-HDMP]CsEu(NO) (), by reacting -3-HDMP and -3-HDMP (where 3-HDMP = 3-hydroxy--dimethylpyrrole) with CsNO and Eu(NO) in a 2:1:1 ratio within an acidic solution. Both -3-HDMPI and -3-HDMPI crystallize in the chiral space group 222 at room temperature, exhibiting a transition from SHG-on to SHG-off (SHG = second harmonic generation) upon heating and cooling. The temperature-dependent X-ray single-crystal diffraction analysis carried out on compound and compound , before and after the phase transition, disclosed the transformation of their space groups from noncentrosymmetric to centrosymmetric. Additionally, the incorporation of rare-earth elements as hybrid B-site cations imparts exceptional fluorescence properties to the compounds. These materials effectively merge the unique characteristics of chiral molecules with the exceptional luminescence of double-perovskite structures, paving the way for innovative optical devices and advanced information processing technologies.
有机-无机杂化手性小分子材料结合了两种组分的固有特性；然而，将手性与稀土双钙钛矿材料相结合的研究却很有限。在这项工作中，我们通过在酸性溶液中以2:1:1的比例使-3-HDMP和-3-HDMP（其中3-HDMP = 3-羟基- -二甲基吡咯）与CsNO₃和Eu(NO₃)₃反应，合成了三维（3D）杂化稀土双钙钛矿的两种对映体，[-3-HDMP]CsEu(NO₃)₄ () 和 [-3-HDMP]CsEu(NO₃)₄ ()。-3-HDMPI和-3-HDMPI在室温下均在手性空间群222中结晶，在加热和冷却时表现出从SHG开启到SHG关闭（SHG = 二次谐波产生）的转变。在相变前后对化合物 和化合物 进行的温度依赖性X射线单晶衍射分析揭示了它们的空间群从非中心对称转变为中心对称。此外，作为杂化B位阳离子掺入的稀土元素赋予了化合物优异的荧光特性。这些材料有效地将手性分子的独特特性与双钙钛矿结构的优异发光特性融合在一起，为创新光学器件和先进信息处理技术铺平了道路。
