Majority-Rule of Enantiomeric Excess in Chiral Halide Perovskites for continuous tuning of chiroptical properties
4 affiliations
- 1Dipartimento di Scienze della Salute, Università “Magna Græcia” di Catanzaro, Viale Europa, Italy, 88100
- 2Laboratory for Energy Materials
- 3Ecole Polytechnique Fédérale de Lausanne
- 4ITODYS
Abstract
Chiral halide perovskites have emerged as promising platform for spin-optoelectronic applications, yet the role of chiral precursor composition in governing their chiroptical properties remains poorly understood. Here, we investigate how enantiomeric excess (ee) controls the chiroptical response of the prototypical two-dimensional (2D) chiral halide perovskite (R/S-MBA)2PbI4 (MBA = methylbenzylammonium) across a compositional series spanning ee = -100% to +100% corresponding to R-MBA mole fractions ranging from 0% to 100%. By combining experimental spectroscopy with first-principles simulations, an approach we demonstrate to be transferable to tin-based analogues as well, we establish a quantitative structure-chiroptical property relationship across the full ee range. Circular dichroism (CD) spectra and absorption dissymmetry factors (gabs) exhibit a progressive, nonlinear evolution with increasing ee, consistent with cooperative majority-rule behavior governing chirality transfer from the organic cation to the inorganic framework. This effect is most pronounced in the 400-450 nm spectral region, where the CD signal tracks enantiomeric composition with high fidelity. Ab initio molecular dynamics coupled with time-dependent density functional theory (TD-DFT) quantitatively reproduces both the experimental CD spectra and gabs values across the entire compositional series, revealing that the macroscopic chiroptical response originates from the collective arrangement of chiral ligands, acting as a continuous dial for simultaneously modulating optical activity. This positions the ee as a general, accessible design parameter for chiroptical engineering across the family of halide perovskites.
Versions
Related
- Chiral Anthranyl Bis-sulfoxides with Modular Chiroptical Properties Controlled by an Ionic Stimulus
- Chiral coronene diimide assemblies with strong chiroptical properties in solution and thin-films.
- Impact of aromatic ether substituents on chiroptical properties in BINOL-based systems
- Conformationally locked planar-chiral single- and double-bridged perylene diimides with highly twisted structures: topology-controlled synthesis and chiroptical properties
- Tuning Chiroptical Properties and Device Hyperfluorescence Efficiency via Acceptor Modification in an Intramolecularly Sensitised TADF Dendrimer
BibTeX
@misc{fortino2026majorityrule,
title = {{Majority-Rule of Enantiomeric Excess in Chiral Halide Perovskites for continuous tuning of chiroptical properties}},
author = {Mariagrazia Fortino and Hongki Kim and Amina Alehyane and Florent Barbault and Antonio Monari and Sascha Feldmann and Adriana Pietropaolo},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009737/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009737/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Majority-Rule of Enantiomeric Excess in Chiral Halide Perovskites for continuous tuning of chiroptical properties
AU - Mariagrazia Fortino
AU - Hongki Kim
AU - Amina Alehyane
AU - Florent Barbault
AU - Antonio Monari
AU - Sascha Feldmann
AU - Adriana Pietropaolo
PY - 2026
DA - 2026/10/01
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009737/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009737/v1
AB - Chiral halide perovskites have emerged as promising platform for spin-optoelectronic applications, yet the role of chiral precursor composition in governing their chiroptical properties remains poorly understood. Here, we investigate how enantiomeric excess (ee) controls the chiroptical response of the prototypical two-dimensional (2D) chiral halide perovskite (R/S-MBA)2PbI4 (MBA = methylbenzylammonium) across a compositional series spanning ee = -100% to +100% corresponding to R-MBA mole fractions ranging from 0% to 100%. By combining experimental spectroscopy with first-principles simulations, an approach we demonstrate to be transferable to tin-based analogues as well, we establish a quantitative structure-chiroptical property relationship across the full ee range. Circular dichroism (CD) spectra and absorption dissymmetry factors (gabs) exhibit a progressive, nonlinear evolution with increasing ee, consistent with cooperative majority-rule behavior governing chirality transfer from the organic cation to the inorganic framework. This effect is most pronounced in the 400-450 nm spectral region, where the CD signal tracks enantiomeric composition with high fidelity. Ab initio molecular dynamics coupled with time-dependent density functional theory (TD-DFT) quantitatively reproduces both the experimental CD spectra and gabs values across the entire compositional series, revealing that the macroscopic chiroptical response originates from the collective arrangement of chiral ligands, acting as a continuous dial for simultaneously modulating optical activity. This positions the ee as a general, accessible design parameter for chiroptical engineering across the family of halide perovskites.
ER -