The First Enantiomeric Stereogenic Sulfur‐Chiral Organic Ferroelectric Crystals

Abstract Chiral ferroelectric crystals with intriguing features have attracted great interest and many with point or axial chirality based on the stereocarbon have been successively developed in recent years. However, ferroelectric crystals with stereogenic heteroatomic chirality have never been documented so far. Here, we discover and report a pair of enantiomeric stereogenic sulfur‐chiral single‐component organic ferroelectric crystals, R s ‐ tert ‐butanesulfinamide ( R s ‐tBuSA) and S s ‐ tert ‐butanesulfinamide ( S s ‐tBuSA) through the deep understanding of the chemical design of molecular ferroelectric crystals. Both enantiomers adopt chiral‐polar point group 2 ( C 2 ) and exhibit mirror‐image relationships. They undergo high‐temperature 432 F 2‐type plastic ferroelectric phase transition around 348 K. The ferroelectricity has been well confirmed by ferroelectric hysteresis loops and domains. Polarized light microscopy records the evolution of the ferroelastic domains, according with the fact that the 432 F 2‐type phase transition is both ferroelectric and ferroelastic. The very soft characteristics with low elastic modulus and hardness reveals their excellent mechanical flexibility. This finding indicates the first stereosulfur chiral molecular ferroelectric crystals, opening up new fertile ground for exploring molecular ferroelectric crystals with great application prospects.