期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 2022, 期 23, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.202200275
关键词
Chiral; Chirality transfer; Circular dichroism; Metal halide; Structural asymmetry
资金
- Hong Kong University of Science and Technology (HKUST) School of Science (SSCI)
- Department of Chemistry [R9270]
- Research Grants Council of Hong Kong via the Early Career Scheme (ECS) [26300721]
Chiral metal-halide hybrids have versatile chemical and structural properties, and understanding the structure-optical activity relationship is crucial for their applications.
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)-(+)-alpha-methylbenzyl-ammonium (R-MBAH(+)) or (R)-(-)-1-cyclohexylethylammonium (R-CHEAH(+)), X = Br, I) and one-dimensional corner-shared (1D, A(2)'SbX5, A' = (R)-(+)-alpha-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.
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