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Title: | Conformer-Mediated Helical Chirality in 2D Layered Hybrid Perovskites |
Authors: | DUTTA, TANIYA Swain, Diptikanta NAG, ANGSHUMAN Dept. of Chemistry |
Keywords: | Chiral hybrid perovskites Conformer-induced chirality Helical chirality Asymmetric non-covalent interactions Chiroptic properties 2025-JAN-WEEK1|TOC-JAN-2025 2024 |
Issue Date: | Dec-2024 |
Publisher: | Wiley |
Citation: | Angewandte Chemie International Edition |
Abstract: | Two-dimensional (2D) chiral hybrid perovskites A2PbI4 (A: chiral organic ion) enable chirality controlled optoelectronic and spin-based properties. A+ organic sublattice induces chirality into the semiconducting [PbI4]2− inorganic sublattice through non-covalent interactions at organic–inorganic interface. Often, the A+ cations in the lattice have different orientations, leading to asymmetry in the non-covalent interactions. In a novel approach, we use different conformers of A+ cations to create asymmetry in the non-covalent interactions, thereby, achieving chiral perovskites with rare helical enantiomorphic structures. We prepared (R-IdPA)2PbI4 and (S-IdPA)2PbI4 (IdPA: 1-iodopropan-2-ammonium) which crystallize in the helical enantiomorphic space groups P43212 and P41212, respectively. The gauche- and anti-conformers of IdPA+ are arranged alternatively in the hybrid structure. Importantly, the anti-conformer of IdPA+ ion have significantly stronger electrostatic, N−H⋅⋅⋅I hydrogen bonding, and I⋅⋅⋅I halogen bonding interactions with the [PbI4]2− sublattice, compared to the gauche-conformer. This periodic asymmetry in non-covalent interactions caused by the alternative arrangement of gauche- and anti-conformers induces chirality in the inorganic sublattice with four-fold screw axes (43 and 41). The enantiomers (R-/S-IdPA)2PbI4 show mirror-image like circular dichroism from excitonic absorption of the inorganic sublattice. This conformer-based design of chiral hybrid perovskites in helical space groups broadens material choices for advanced optoelectronic applications. |
URI: | https://doi.org/10.1002/anie.202422550 http://dr.iiserpune.ac.in:8080/xmlui/handle/123456789/9279 |
ISSN: | 1433-7851 1521-3773 |
Appears in Collections: | JOURNAL ARTICLES |
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