Three-Dimensional Perovskite Phase Transition Materials with Switchable Second Harmonic Generation Properties...

Switchable second harmonic generation (SHG) materials have potential applications in information storage, signal processing, and so on because they can switch between SHG-on and SHG-off states. In this work, we designed and synthesized three organic-inorganic hybrid Rb halide three-dimensional (3D) perovskite materials [1S,4S 2,5-2.2.1-H₂dabch]RbX₃·0.5H₂O (X = Cl, 1; Br, 2; I, 3) based on the chiral 1S,4S-2,5-diazabicyclo[2.2.1]heptane (1S,4S-2,5-2.2.1-dabch). The selection of homochiral organic cations ensures that the compounds 1∼3 crystallize in the noncentrosymmetric and chiral space group P2₁2₁2₁, which further leads to reversible SHG responses of the three compounds. Through differential scanning calorimetry (DSC) and dielectric measurements, it revealed that the phase transition point of the compounds 1∼3 increased with RbCl, RbBr, and RbI. This is because the hydrogen interaction H···X between the inorganic framework [RbX₃] and the organic cation [1S,4S-2,5-2.2.1-H₂dabch]²⁺ is increased with the order of I > Br > Cl. This study can provide an effective molecular design strategy for the exploration and construction of temperature-tunable SHG switching materials.