Please use this identifier to cite or link to this item: http://dr.iiserpune.ac.in:8080/xmlui/handle/123456789/9279
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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