Bismuth‐Based Chiral Perovskite with Different Dimensions for Second‐Order Nonlinear Optical Properties
Shuang Jiang, Peisheng Zhao, Guoxiang Xing, Huimin Kang, Xiaolei Li, Tianzhe Zhao, Bin Li, Tianyong Zhang
Abstract
Abstract Chiral perovskites have various applications in nonlinear optics due to their asymmetric structures. Currently, nonlinear optical studies have focused on lead‐based perovskite. However, the toxic element, Pb, hinders their further applications. Herein, (R/S‐MBA) 4 Bi 2 Br 10 (MBA = α‐phenylethylamine) and (R/S‐MPA) 2 BiBr 5 (MPA = 1‐phenylpropan‐1‐amine) crystals were synthesized and explored about the nonlinear optics. Both pairs of chiral perovskite enantiomers exhibit good thermal stability and symmetric circular dichroism signals. Interestingly, MPA and MBA differ by only one methylene but show significant differences in the crystal structures synthesized under the same conditions. The (R/S‐MBA) 4 Bi 2 Br 10 crystal is a zero‐dimensional (0D) structure in which the [Bi 2 Br 10 ] 4– dimer is spaced by an organic amine. (R/S‐MPA) 2 BiBr 5 crystals are 1D structures in which [BiBr 6 ] 2– units form infinitely extended chains by angle sharing. The crystals exhibit efficient second harmonic generation response, and the intensity of (R‐MPA) 2 BiBr 5 is four times that of (R‐MBA) 4 Bi 2 Br 10 at 980 nm excitation wavelength. The 1D infinitely extended inorganic chain in (R‐MPA) 2 BiBr 5 allows for a more regular arrangement of chiral organic amines, and adjacent organic amines are arranged differently, together leading to its stronger non‐centrosymmetry, which is the decisive factor of nonlinear optics. The study guides the design and deep research of novel second‐order nonlinear optical materials.