Chiral Zn‐Based Organic‐Inorganic Hybrid Ferroelectrics with Large Polarization and Luminescence

Abstract Multi‐functionalized lead‐free organic‐inorganic hybrid ferroelectrics have recently realized diverse applications especially for optoelectronics and photovoltaics. Herein, the chiral Zn‐based organic−inorganic hybrids are discovered: [(R)‐(−)‐2‐methylpiperazine‐1,4‐diium][Zn(H 2 O) 6 ]•(SO 4 ) 2 (RMPZnS 2 , space group P 2 1 ) and [(S)‐(+)‐2‐methylpiperazine‐1,4‐diium] 2 [Zn(H 2 O) 6 ]•(SO 4 ) 3 (SMP 2 ZnS 3 , space group P 2 1 2 1 2). Through experimental and computational investigations, it is found that RMPZnS 2 is a ferroelectric with considerable large polarization value ( P ≈ 9.5 µC cm −2 ) along b –axis, and its ferroelectric‐paraelectric phase transition is switched by rotation of organic cations. Meanwhile, it also possesses a fascinating photovoltaic effect driven by the polar charges at solar‐blind UV region, endowing it with the potential of self‐driven photodetection. In addition, white‐light emissions of the RMPZnS 2 and SMP 2 ZnS 3 are observed. The enhanced luminescence by heating is especially suitable for the application in white light‐emitting diodes. Overall, these chiral emission ferroelectrics at the supramolecular level will largely expand their applications in multidisciplinary fields.