Charge-Encoded Anion Sublattices Drive Ordering and Phase Selection in Layered Chalcogenides
4 affiliations
- 1Department of Chemistry
- 2Pennsylvania State University
- 3Department of Mechanical and Materials Engineering
- 4Portland State University
Abstract
Predicting the sites where anions order in a crystal, and when that ordering drives structural rearrangement, remains a challenge in mixed-anion chemistry. Here we show that both are linked to the distribution of charge on the anion sublattice of ACuMIVQ3 chalcogenides. Bader analysis of four competing polymorphs reveals that the sequencing of polyhedra controls the range of charge across anion sites (Δq) and programs each structure with a distinct charge-encoded anion sublattice. Thirteen new mixedchalcogen compounds were prepared, and the anion site occupancies were determined through single crystal X-ray diffraction. While sulfoselenides tend to adopt structures with small Δq, where they form near-ideal solid solutions, greater anion disparity in the selenotellurides and sulfotellurides leads to enhanced ordering, which drives formation of alternate structures with higher Δq. These structures provide terraced charge landscapes with more strongly differentiated sites, suggesting that structure selection depends on how well the anion sublattice matches the chemical disparity of the anion mixture. This trend culminates in KCuZrTeSeS, where S, Se, and Te order across three distinct sites in the Pnma structure, a phase not adopted by any single-anion end member, and the first demonstration of site-selective ordering of all three chalcogens in a single material. An enrichment factor connecting site occupancy with Bader charge further shows that the most electronegative chalcogen in a given mixture preferentially occupies the highest-charge site. Together, the results establish charge-encoded anion sublattices as a framework for predicting anion ordering and phase selection in extended solids.
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BibTeX
@misc{tassanov2026chargeencoded,
title = {{Charge-Encoded Anion Sublattices Drive Ordering and Phase Selection in Layered Chalcogenides}},
author = {Ayat Tassanov and Huiju Lee and Keela K. Zambre and Pedro R. Trinidad-Pérez and Yi Xia and James M Hodges},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15009583/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009583/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Charge-Encoded Anion Sublattices Drive Ordering and Phase Selection in Layered Chalcogenides
AU - Ayat Tassanov
AU - Huiju Lee
AU - Keela K. Zambre
AU - Pedro R. Trinidad-Pérez
AU - Yi Xia
AU - James M Hodges
PY - 2026
DA - 2026/09/28
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009583/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009583/v1
AB - Predicting the sites where anions order in a crystal, and when that ordering drives structural rearrangement, remains a challenge in mixed-anion chemistry. Here we show that both are linked to the distribution of charge on the anion sublattice of ACuMIVQ3 chalcogenides. Bader analysis of four competing polymorphs reveals that the sequencing of polyhedra controls the range of charge across anion sites (Δq) and programs each structure with a distinct charge-encoded anion sublattice. Thirteen new mixedchalcogen compounds were prepared, and the anion site occupancies were determined through single crystal X-ray diffraction. While sulfoselenides tend to adopt structures with small Δq, where they form near-ideal solid solutions, greater anion disparity in the selenotellurides and sulfotellurides leads to enhanced ordering, which drives formation of alternate structures with higher Δq. These structures provide terraced charge landscapes with more strongly differentiated sites, suggesting that structure selection depends on how well the anion sublattice matches the chemical disparity of the anion mixture. This trend culminates in KCuZrTeSeS, where S, Se, and Te order across three distinct sites in the Pnma structure, a phase not adopted by any single-anion end member, and the first demonstration of site-selective ordering of all three chalcogens in a single material. An enrichment factor connecting site occupancy with Bader charge further shows that the most electronegative chalcogen in a given mixture preferentially occupies the highest-charge site. Together, the results establish charge-encoded anion sublattices as a framework for predicting anion ordering and phase selection in extended solids.
ER -