Atomistic modeling of lead- and tin-based chiral hybrid perovskites

Mariagrazia Fortino^a, Adriana Pietropaolo^a, Alessandro Mattoni^b

^aDipartimento di Scienze della Salute, Università di Catanzaro, Catanzaro, CZ, Italy

^bIstituto Officina dei Materiali (CNR-IOM), Unità di Cagliari, Cittadella Universitaria, Monserrato, CA, Italy.

Proceedings of MATSUS Fall 2024 Conference (MATSUSFall24)

#ChiNano - Exploring Chiral Nanostructured Materials and Plasmonics for Energy applications

Lausanne, Switzerland, 2024 November 12th - 15th

Organizers: Sascha Feldmann, Magalí Lingenfelder and Giulia Tagliabue

Oral, Mariagrazia Fortino, presentation 188
Publication date: 28th August 2024

Hybrid organic–inorganic perovskites (HOIPs) have emerged as excellent materials for solar cell applications. Indeed, their extreme tunability and facile synthesis have opened the door to many new applications. Chiral HOIPs are attracting great interest as promising frameworks for chiroptoelectronics as well as spintronics applications.^[1,2] The chiroptical properties observed in chiral HOIPs can be explained understanding the chirality transfer from the chiral organic molecules to the achiral inorganic octahedra. A key element of the chirality transfer mechanism involves the distortion of the coordination geometry of the inorganic octahedra induced by the presence of chiral ligands.In this study, we propose a tailored simulation workflow based on Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT)^[3] to theoretically explore the chirality transfer mechanism and the chiroptical properties of chiral HOIPs. To this aim, we investigate the chiroptical response of lead- and tin-based 2D chiral perovskites, specifically 2D R- and S-(MBA+)2PbI4^[4]and R- and S-(MBA+)2SnI4.^[5] We explore the most impactful factors influencing their Circular Dichroism (CD) signals through ab-initio molecular dynamics simulations and the analysis of the density of electronic states (DOSs). Our findings reveal that the relevant chiroptical features are linked to a chirality transfer event driven by a metal–ligand overlap of electronic levels. This effect is more evident for tin-based chiral perovskites showing higher excitonic coupling.

References:

[1] Pietropaolo A.; Mattoni A.; Pica G.; Fortino M.;Schifino G.;Grancini G. Rationalizing the design and implementation of chiral hybrid perovskites. Chem 2022, 8, 1231

[2] Duim, H.; Loi, M. A. Chiral hybrid organic-inorganic metal halides: A route toward direct detection and emission of polarized light. Matter 2021, 4, 3835.

[3] Fortino, M.; Mattoni, A.; Pietropaolo, A. Atomistic modeling of metal–ligand chirality transfer and chiroptical properties of lead and tin hybrid perovskites. J. Mater. Chem. C 2023, 11, 9135.

[4] Ma, J.; Fang, C.; Chen, C.; Jin, L.; Wang, J.; Wang, S.; Tang, J.; Li, D. Chiral 2D Perovskites with a High Degree of Circularly Polarized Photoluminescence. ACS Nano 2019, 13, 3659.

[5] Lu, H.; Xiao, C.; Song, R.; Li, T.; Maughan, A. E.; Levin, A.; Brunecky, R.; Berry, J. J.; Mitzi, D. B.; Blum V.; Beard, M.C. Highly Distorted Chiral Two-Dimensional Tin Iodide Perovskites for Spin Polarized Charge Transport. J. Am. Chem. Soc. 2020, 142, 13030.

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