Narrowband Emitting Tin Dion-Jacobson Perovskites through Systematic Spacer Cation Design to Suppress Metal Lone-Pair Anisotropy.
- 1Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin53706, United States.
- 2Wright Center for Photovoltaics Innovation and Commercialization, Department of Physics and Astronomy, University of Toledo, Toledo, Ohio43606, United States.
- 3Department of Industrial Chemistry Toso Montanari, University of Bologna, Bologna40129, Italy.
Abstract
Two-dimensional (2D) Dion-Jacobson (DJ) tin perovskites are promising lead-free semiconductors, yet the limited number of phases reported and their frequently broad and asymmetric photoluminescence (PL) have hindered mechanistic understanding and rational design of their optoelectronic properties. Here, we systematically study 13 DJ Pb/Sn iodide perovskite pairs with identical diammonium spacer cations, including four newly synthesized Sn phases, to seek structure-property trends. We show that narrow and symmetric PL of Pb perovskites alone does not predict similarly favorable emission from Sn analogues. Instead, Sn DJ perovskites with narrow and symmetric PL share a structural motif defined by crystallographically equivalent perovskite pockets and minimal metal off-centering distortion, which can be achieved by symmetric spacer cations. First-principles calculations together with symbolic regression quantitatively connect this motif to reduced anisotropy of the Sn2+ lone pair expression and smaller excited-state structural reorganization, consistent with suppressed vibronic broadening of PL peaks. These structural and electronic criteria guide the identification and synthesis of (4F-PDMA)SnI4 (4F-PDMA = 2,3,5,6-tetrafluoro-1,4-phenylenedimethanammonium) that exhibits anticipated structural features, favorable PL characteristics, and excellent stability. This work introduces a rational spacer cation design strategy to suppress metal lone-pair anisotropy and achieve tin DJ perovskites with narrow PL emission for future high-performance optoelectronic applications.
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BibTeX
@article{forlano2026narrowband,
title = {{Narrowband Emitting Tin Dion-Jacobson Perovskites through Systematic Spacer Cation Design to Suppress Metal Lone-Pair Anisotropy.}},
author = {Kristel M Forlano and Jiahao Xie and Christopher T Triggs and Jalianet Román-Matías and Daniel D Kohler and Francesca Canestra and Cristina Femoni and David P Lafayette and Ilia A Guzei and Daniele Cortecchia and John C Wright and Yanfa Yan and Song Jin},
journal = {Journal of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/jacs.6c11969},
url = {https://europepmc.org/article/MED/42913584},
note = {CC BY},
}
RIS
TY - JOUR
TI - Narrowband Emitting Tin Dion-Jacobson Perovskites through Systematic Spacer Cation Design to Suppress Metal Lone-Pair Anisotropy.
AU - Kristel M Forlano
AU - Jiahao Xie
AU - Christopher T Triggs
AU - Jalianet Román-Matías
AU - Daniel D Kohler
AU - Francesca Canestra
AU - Cristina Femoni
AU - David P Lafayette
AU - Ilia A Guzei
AU - Daniele Cortecchia
AU - John C Wright
AU - Yanfa Yan
AU - Song Jin
PY - 2026
DA - 2026/10/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c11969
UR - https://europepmc.org/article/MED/42913584
AB - Two-dimensional (2D) Dion-Jacobson (DJ) tin perovskites are promising lead-free semiconductors, yet the limited number of phases reported and their frequently broad and asymmetric photoluminescence (PL) have hindered mechanistic understanding and rational design of their optoelectronic properties. Here, we systematically study 13 DJ Pb/Sn iodide perovskite pairs with identical diammonium spacer cations, including four newly synthesized Sn phases, to seek structure-property trends. We show that narrow and symmetric PL of Pb perovskites alone does not predict similarly favorable emission from Sn analogues. Instead, Sn DJ perovskites with narrow and symmetric PL share a structural motif defined by crystallographically equivalent perovskite pockets and minimal metal off-centering distortion, which can be achieved by symmetric spacer cations. First-principles calculations together with symbolic regression quantitatively connect this motif to reduced anisotropy of the Sn2+ lone pair expression and smaller excited-state structural reorganization, consistent with suppressed vibronic broadening of PL peaks. These structural and electronic criteria guide the identification and synthesis of (4F-PDMA)SnI4 (4F-PDMA = 2,3,5,6-tetrafluoro-1,4-phenylenedimethanammonium) that exhibits anticipated structural features, favorable PL characteristics, and excellent stability. This work introduces a rational spacer cation design strategy to suppress metal lone-pair anisotropy and achieve tin DJ perovskites with narrow PL emission for future high-performance optoelectronic applications.
SN - 0002-7863
SN - 1520-5126
ER -