Second-harmonic generation (SHG) is one of the outstanding properties for practical applications. However, the great majority of molecular ferroelectric materials have very low nonlinear optical coefficients, attenuating their attractive performance. Here we synthesized (4-amino-2-bromopyridinium)(4-amino-2-bromopyridine)tetrafluoroborate (1), whose second-order nonlinear optical coefficient reaches up to 2.56 pm V(-1), 2.67 times of that of KDP, and (4-amino-2-bromopyridinium)tetrafluoroborate (2), possessing a more incredible large second-order nonlinear optical coefficient as high as 10.24 pm V(-1), 10.67 times that of KDP. The compound 1 undergoes two reversible phase transitions at around T1 = 244.1 K and T2 = 154.6 K, caused by dramatic changes of the protonated cations and order-disorder of anions, which was disclosed by differential scanning calorimetry, heat capacity, dielectric anomalies, SHG, and single-crystal X-ray diffraction analysis. The pyroelectric measurements reveal that compound 1 is a Rochelle salt type ferroelectric, which has a large spontaneous polarization of about 3 μC/cm(2).

Diisopropylammonium bromide (DIPAB) has attracted great attention as a molecular ferroelectric with large spontaneous polarization and high Curie temperature. It is hard to grow the ferroelectric phase DIPAB because of the appearance of the non-ferroelectric phase DIPAB at room temperature. Here, a ferroelectric thin film of DIPAB was successfully fabricated on a Si substrate using a spin coating method from aqueous solution via 12-crown-4 addition at room temperature. The ferroelectric DIPAB film with a thickness of hundreds of nanometers is distributed discontinuously on the substrate in narrow strips. The direction of polarization is along the narrow strip. Piezoresponse force microscopy (PFM) shows that the ferroelectric films have two kinds of domain structures: noncharged antiparallel stripe domains and charged head-to-head (H-H)/tail-to-tail (T-T) type domains. 12-crown-4 has been proved to play important roles in forming the H-H/T-T type domains. The Chynoweth method shows that the DIPAB films synthesized in this way show a better pyroelectric effect than DIPAB crystals.

A new molecular ferroelectric is discovered in an organic–inorganic hybrid compound, (C6H5NH3)2CdCl4, which undergoes a reversible order–disorder ferroelectric phase transition at 369 K.