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Structural Asymmetry and Chiroptical Activity of Chiral Antimony‐Halide Hybrids

Zhiyu Wang, Zixuan Zhang, Herman H. Y. Sung, Ian D. Williams, Haipeng Lu

2022European Journal of Inorganic Chemistry22 citationsDOI

Abstract

Abstract Chiral metal‐halide hybrids have aroused widespread attention owing to their chemical and structural versatilities as well as unique optoelectronic and spin‐dependent properties. Several recent experiments have shown that organic chirality results in circularly polarized absorption and emission from the inorganic metal‐halide subcomponent; however, the exact structure chirality transfer mechanism and structure‐optical‐activity relation remain elusive. Here, we demonstrate how chiral organic cations lead to local structural asymmetry in a new series of chiral antimony‐halide hybrids, including zero‐dimensional edge‐shared (0D, A 4 Sb 2 X 10 , A=( R )‐(+)‐α‐methylbenzylammonium ( R ‐MBAH + ) or ( R )‐(−)‐1‐cyclohexylethylammonium ( R ‐CHEAH + ), X=Br, I) and one‐dimensional corner‐shared (1D, A’ 2 SbX 5 , A’=( R )‐(+)‐α‐ethylbenzylammonium ( R ‐EBAH + ); X=Br, I). Structure analysis shows that organic ammoniums distort the antimony‐halide octahedra through asymmetric hydrogen bonding. The chiroptical activity is correlated with the exciton coupling strength, which can be tuned by the structural dimensionality. Our study unveils the molecular scale chirality transfer mechanism in these chiral metal‐halide hybrids.

Topics & Concepts

ChemistryChirality (physics)HalideAsymmetryCrystallographyMetal halidesChemical physicsPhotochemistryStereochemistryComputational chemistryInorganic chemistryPhysicsNambu–Jona-Lasinio modelChiral symmetry breakingQuarkQuantum mechanicsPerovskite Materials and ApplicationsSolid-state spectroscopy and crystallographyCrystal Structures and Properties
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