The First 2D Homochiral Lead Iodide Perovskite Ferroelectrics: [R- and S-1-(4-Chlorophenyl)ethylammonium]2 PbI4.

2D organic-inorganic lead iodide perovskites have recently received tremendous attention as promising light absorbers for solar cells, due to their excellent optoelectronic properties, structural tunability, and environmental stability. However, although great efforts have been made, no 2D lead iodide perovskites have been discovered as ferroelectrics, in which the ferroelectricity may improve the photovoltaic performance. Here, by incorporating homochiral cations, 2D lead iodide perovskite ferroelectrics [R-1-(4-chlorophenyl)ethylammonium]2 PbI4 and [S-1-(4-chlorophenyl)ethylammonium]2 PbI4 are successfully obtained. The vibrational circular dichroism spectra and crystal structural analysis reveal their homochirality. They both crystalize in a polar space group P1 at room temperature, and undergo a 422F1 type ferroelectric phase transition with transition temperature as high as 483 and 473.2 K, respectively, showing a multiaxial ferroelectric nature. They also possess semiconductor characteristics with a direct bandgap of 2.34 eV. Nevertheless, their racemic analogue adopts a centrosymmetric space group P21 /c at room temperature, exhibiting no high-temperature phase transition. The homochirality in 2D lead iodide perovskites facilitates crystallization in polar space groups. This finding indicates an effective way to design high-performance 2D lead iodide perovskite ferroelectrics with great application prospects.

Directional Intermolecular Interactions for Precise Molecular Design of a High- Tc Multiaxial Molecular Ferroelectric.

Quasi-spherical molecules have recently been developed as promising building blocks for constructing high-performance molecular ferroelectrics. However, although the modification of spherical molecules into quasi-spherical ones can efficiently lower the crystal symmetry, it is still a challenge to precisely arouse a low-symmetric polar crystal structure. Here, by introducing directional hydrogen-bonding interactions in the molecular modification, we successfully reduced the cubic centrosymmetric Pm3̅ m space group of [quinuclidinium]ClO4 at room temperature to the orthorhombic polar Pna21 space group of [3-oxoquinuclidinium]ClO4. Different from the substituent groups of -OH, -CH3, and ═CH2, the addition of a ═O group with H-acceptor to [quinuclidinium]+ forms directionally N-H···O═C hydrogen-bonded chains, which plays a critical role in the generation of polar structure in [3-oxoquinuclidinium]ClO4. Systematic characterization indicates that [3-oxoquinuclidinium]ClO4 is an excellent molecular ferroelectric with a high Curie temperature of 457 K, a large saturate polarization of 6.7 µC/cm2, and a multiaxial feature of 6 equiv ferroelectric axes. This work demonstrates that the strategy of combining quasi-spherical molecule building blocks with directional intermolecular interactions provides an efficient route to precisely design new eminent molecular ferroelectrics.