No abstract

2D hybrid lead halide perovskites exhibit versatile photoluminescent behaviors for narrowband to broadband emissions (BBEs) and have become attractive candidates for potential applications such as solid-state lighting. Establishing the relationship between the perovskite structural distortion and BBE is key but challenging in designing and optimizing the perovskite luminophores. Conventional attention is given to analyzing the intra-octahedron distortion of the [PbX6]4– (X = halide) unit that has not yet provided a clear structure–luminescence relationship. Herein, we introduce a descriptor, Pb displacement, to describe the inter-octahedron distortion to clarify the structure–emission relationship. The displacement of adjacent Pb centers represents the lattice distortion, which determines the broadband/narrowband emission instead of the octahedron distortion itself. We find a kite-type quadrilateral rule in (001) type 2D perovskites, that is, the degree to which the four octahedral central ions deviate from a square relates to the BBE. The kite-type arrangement of the Pb ions usually corresponds to the BBEs due to the large structure distortions. In contrast, the square-type arrangement of the Pb ions corresponds to the narrowband emissions because of the small distortions. The distortion descriptor magnifies the distortion scale, making it larger than the conventional one for the intra-octahedron distortion, which matches the general concept of excitons based on the scale of the crystal lattice. Therefore, the set of structural descriptors is better to correlate the perovskite structures and emission properties.

Direct detection of circularly polarized light (CPL) is a challenging task due to limited materials and ambiguous structure–property relationships that lead to low distinguishability of the light helicities. Perovskite ferroelectric semiconductors incorporating chirality provide new opportunities in dealing with this issue. Herein, a pair of 2D chiral perovskite ferroelectrics is reported, which have enhanced CPL detection performance due to interplays among lattice, photon, charge, spin, and orbit. The chirality‐transfer‐induced chiral&polar ferroelectric phase enhances the asymmetric nature of the photoactive sublattice and achieves a switchable self‐powered detection via the bulk photovoltaic effect. The single‐crystal‐based device exhibits a CPL‐sensitive detection performance under 430 nm with an asymmetric factor of 0.20 for left‐ and right‐CPL differentiation, about two times that of the pure chiral counterparts. The enhanced CPL detection performance is ascribed to the Rashba–Dresselhaus effect that originates from the bulk inversion asymmetry and strong spin–orbit coupling, shown with a large Rashba coefficient, which is demonstrated by density functional theory calculation and circularly polarized light excited photoluminescence measurement. These results provide new perspectives on chiral Rashba ferroelectric semiconductors for direct CPL detection and ferroelectrics‐based chiroptics and spintronics.

A series of oxygen reduction redox mediators (ORRMs) based on anthraquinone (AQ) has been developed for the lithium–oxygen (Li–O2) battery on the basis of a strategy to control the reduction potentials of the AQ moiety. It was found that the discharge capacity of the Li–O2 battery can be significantly improved by introducing electron-withdrawing groups into the AQ moiety, which can positively move the reduction potential of the AQ derivatives. By the introduction of two nitro (NO2) groups to the AQ moieties, an approximate 45-fold increase in the discharge capacity has been realized with a high discharge potential. Furthermore, we found that the water molecule from the oxygen environment exhibits a dramatic synergistic effect with the ORRM on the discharge capacity of the Li–O2 battery.

Ferroic phase transition molecular crystals (FPTMCs), i.e., ferroelectrics and ferroelastics, are an important family of functional molecular materials, having merits of easy synthesis, structural tunability and flexibility, and biocompatibility. Both...