Molecular Ferroelectric [(NMe2)3PCH2Cl]PbI3 Showing Two-Step Switching Second-Order Nonlinear Optics

Molecular ferroelectrics have garnered significant attention owing to their environmental compatibility, facile synthesis, lightweight nature, and structural versatility. In this study, we present a novel one-dimensional (1D) organic–inorganic hybrid perovskite molecular ferroelectric, [(NMe2)3PCH2Cl]PbI3 (1), which undergoes two successive reversible phase transitions. This compound demonstrates distinct spontaneous polarization in ferroelectric domains, along with two-step switching in second-harmonic generation (SHG) and dielectric responses. Variable-temperature single-crystal X-ray diffraction reveals a symmetry-breaking transition in 1, shifting from the centrosymmetric P63/mmc space group to the polar noncentrosymmetric P63 ferroelectric phase. This transition is primarily driven by an order–disorder transformation of the [(NMe2)3PCH2Cl]+ cation. Furthermore, compound 1 exhibits promising semiconductor characteristic with a bandgap of 2.70 eV. This material’s unique high-low-off SHG-switching behavior and robust polarization switching (Ps = 0.3 μC·cm–2) position it as a multifunctional platform for next-generation applications in multistate memory devices, programmable optical modulators, and temperature-responsive sensors, addressing critical limitations of conventional molecular ferroelectrics in stability and functional diversity.