Two 3D Rare-Earth Double Perovskite Materials Constructed with a Pair of Enantiomers

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, [<i>R</i>-3-HDMP]₂CsEu(NO₃)₆ (<b>1</b>) and [<i>S</i>-3-HDMP]₂CsEu(NO₃)₆ (<b>2</b>), by reacting <i>R</i>-3-HDMP and <i>S</i>-3-HDMP (where 3-HDMP = 3-hydroxy-<i>N,N</i>-dimethylpyrrole) with CsNO₃ and Eu(NO₃)₃ in a 2:1:1 ratio within an acidic solution. Both <i>R</i>-3-HDMPI and <i>S</i>-3-HDMPI crystallize in the chiral space group <i>P</i>2₁2₁2₁ 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 <b>1</b> and compound <b>2</b>, 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.