Chiral Fluorine Engineering in Amine Molecular Design: Toward High‐ T c Multifunctional Rare‐Earth Hybrid Double Perovskites

作者：Xiao Sun, Yuting Li, Xin Yin, Zhenhong Wei, Hu Cai · 发表于：Small · 年份：2025 · DOI：10.1002/smll.202505444 · 被引用次数：5 · 研究领域：Perovskite Materials and Applications、Magnetism in coordination complexes、Solid-state spectroscopy and crystallography

Abstract Chiral organic‐inorganic hybrid rare‐earth double perovskites represent an emerging multidisciplinary frontier that synergizes structural diversity, rare‐earth functionalities, and chirality‐driven phenomena. In this study, a chiral F‐engineering strategy is developed to synthesize three novel hybrid double perovskites: ( Rac ‐3‐DMFP) 2 RbEu(NO 3 ) 6 ( Rac ‐1 ) and its enantiopure analogues ( R / S ‐3‐DMFP) 2 RbEu(NO 3 ) 6 ( R / S ‐1 ). The intrinsic chirality of enantiomers R ‐1 and S‐ 1 is unambiguously confirmed by vibrational circular dichroism (VCD) spectroscopy. Compared to the racemic Rac ‐1 , the enantiomeric R / S ‐1 pair exhibits enhanced functionalities, including reversible phase transitions at elevated temperatures, distinct dielectric anomalies, and superior second‐harmonic generation (SHG) responses with SHG intensities surpassing those of conventional NO 3 − ‐based perovskites. Comprehensive optoelectronic characterization leveraging the f‐f transition of Eu 3+ ions revealed broad UV absorption (250–400 nm), intense red luminescence ( 5 D 0 → 7 F 2 at 615 nm), a prolonged fluorescence lifetime ( τ = 3.89 ms), and a notable quantum yield ( Φ = 32.23%). This work establishes an effective molecular design strategy for exploring and constructing multifunctional organic‐inorganic hybrid rare‐earth double perovskites, highlighting their potential in advanced optoelectronics and nonlinear optical technologies.