Haque Md Azimul, Grieder Andrew, Harvey Steven P, Brunecky Roman, Ye Jiselle Y, Addison Bennett, Zhang Junxiang, Dong Yifan, Xie Yi, Hautzinger Matthew P, Walpitage Heshan Hewa, Zhu Kai, Blackburn Jeffrey L, Vardeny Zeev Valy, Mitzi David B, Berry Joseph J, Marder Seth R, Ping Yuan, Beard Matthew C, Luther Joseph M
National Renewable Energy Laboratory, Golden, CO, USA.
Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, WI, USA.
Nat Chem. 2025 Jan;17(1):29-37. doi: 10.1038/s41557-024-01662-2. Epub 2024 Oct 25.
In hybrid metal halide perovskites, chiroptical properties typically arise from structural symmetry breaking by incorporating a chiral A-site organic cation within the structure, which may limit the compositional space. Here we demonstrate highly efficient remote chirality transfer where chirality is imposed on an otherwise achiral hybrid metal halide semiconductor by a proximal chiral molecule that is not interspersed as part of the structure yet leads to large circular dichroism dissymmetry factors (g) of up to 10. Density functional theory calculations reveal that the transfer of stereochemical information from the chiral proximal molecule to the inorganic framework is mediated by selective interaction with divalent metal cations. Anchoring of the chiral molecule induces a centro-asymmetric distortion, which is discernible up to four inorganic layers into the metal halide lattice. This concept is broadly applicable to low-dimensional hybrid metal halides with various dimensionalities (1D and 2D) allowing independent control of the composition and degree of chirality.
在混合金属卤化物钙钛矿中,手性光学性质通常源于通过在结构中引入手性A位有机阳离子而导致的结构对称性破缺,这可能会限制组成空间。在此,我们展示了高效的远程手性转移,即通过一个近端手性分子将手性施加到原本非手性的混合金属卤化物半导体上,该手性分子并非作为结构的一部分穿插其中,但却能导致高达10的大的圆二色性不对称因子(g)。密度泛函理论计算表明,立体化学信息从手性近端分子向无机骨架的转移是由与二价金属阳离子的选择性相互作用介导的。手性分子的锚定诱导了中心不对称畸变,这种畸变在金属卤化物晶格中深入到四个无机层都可辨别。这一概念广泛适用于具有各种维度(1D和2D)的低维混合金属卤化物,允许对组成和手性程度进行独立控制。