Boosted Second Harmonic Generation of a Chiral Hybrid Lead Halide Resonant to Charge Transfer Exciton from Metal Halide Octahedra to Ligand.

Chiral hybrid organic-inorganic metal halides (HOMHs) offer an ideal platform for the advancement of second-order nonlinear optical (NLO) materials owing to their inherent noncentrosymmetric structures. The enhancement of optical nonlinearity of chiral HOMHs could be achieved by matching the free exciton and/or self-trapped exciton energy levels with desired NLO frequencies. However, the current scarcity of resonance modes and low resonance ratio hamper the further improvements of NLO performance. Herein, we propose a new resonant channel of charge transfer (CT) excited states from metal halide polyhedra to organic ligand to boost the second-order optical nonlinearity of chiral HOMHs. The model lead halide (C7H10N)PbBr3 (C7H10N=1-ethylpyridinium) exhibits a drastically enhanced second harmonic generation in resonance to the deep CT exciton energy, with intensity of up to 111.0 times that of KDP and 10.9 times that of urea. The effective NLO coefficient has been determined to be as high as ~40.2 pm V-1, balanced with a large polarization ratio and high laser damage threshold. This work highlights the contribution of organic ligands in the construction of a resonant channel for enhancing second-order NLO coefficients of metal halides, and thus provides guidelines for designing new chiral HOMHs materials for advanced nonlinear photonic applications.

Dielectric phase transition of an A2BX4-type perovskite with a pentahedral to octahedral transformation.

Organic-inorganic hybrid compounds that undergo reversible dielectric phase transitions are a very attractive class of smart materials due to their wide applications in data storage, data communication and signal sensing. Here, a piperidine ring, C5H11N, was introduced into the inorganic lead halide perovskite scaffold to obtain three hybrid perovskite compounds, [C5H12N]2PbCl4 (1), [C5H12N]2PbBr4 (2), and [C5H12N]PbI3 (3). When compound 2 and compound 3 feature static two-dimensional (2D) and one-dimensional (1D) perovskite structures, respectively, it is striking that compound 1 shows a reversible pentahedral to octahedral transformation. It undergoes an above-room-temperature dielectric phase transition at Tc≅ 352 K, wherein the high dielectric constant is more than twice the low dielectric constant. Structural analysis shows that 1 undergoes a phase transition from the space group Pnma at the low temperature phase (LTP) to C2/c at the high temperature phase (HTP). The phase transition originates from the order-disorder conversion of piperidinium cations. It is interesting to note that, the Pb2+ cations in the inorganic moieties change from five-coordinate at the LTP to six-coordinate at the HTP. The discovery of dielectric phase transition hybrid organic-inorganic lead halide perovskite materials further enhances the potential applications of high temperature responsive dielectric switchable materials.