A Metal‐Free Molecular Ferroelectric [4‐Me‐cyclohexylamine]ClO4 Introduced by Boat and Chair Conformations of Cyclohexylamine

Abstract Organic ferroelectrics have received a great deal of interest due to their exclusive properties. However, organic ferroelectrics have not been fully explored, which hinders their practical application. Here, we presented a novel metal‐free organic molecular ferroelectric [4‐MCHA][ClO 4 ] ( 1 ) (4‐MCHA= trans ‐4‐methylcyclohexylamine), which exhibits an above‐room‐temperature of 328 K. Strikingly, the single crystal structure analysis of 1 shows that the driving force of phase transition is related to the interesting chair‐boat conformation change of 4‐MCHA cation, in addition to the order‐disorder transition of ClO 4 − anion. Using piezoelectric response force microscopy (PFM), the presence of domains and the implemented polarization switching were clearly observed, which explicitly determined the presence of room‐temperature ferroelectricity of 1 . As far as we know, the ferroelectric phase transition mechanism attributed to the conformational change in a trans isomeric cation is very rare. This research enriched the path of designing ferroelectric materials and smart materials.