Rational Pathways to Ordered Multianion Chalcogenides Using Retrosynthetic Crystal Chemistry

Mixed-anion chalcogenides make up a versatile class of materials with properties that can be fine-tuned for specific applications. While chalcogen anions (Q = S, Se, or Te) tend to form solid solutions in simple binary systems, ordering does occur in structures that have more than one unique anion site. Here, we use crystallographic analysis and hard-soft acid-base principles to predict the Wyckoff positions that secondary chalcogens will occupy in a range of single-anion hosts. The analysis serves as a guide for generating ordered sulfoselenide, selenotelluride, and sulfotelluride products in a predictable manner. The study focuses on ternary and quaternary systems with varying compositional and structural features, with an emphasis on 3D CsCu₅Q₃ (P4₂/mnm) and 2D NaCuZrQ₃ (Pnma) crystal systems. The samples were prepared by using high-temperature solid-state methods and structurally characterized by using single-crystal X-ray diffraction. Ordering in the mixed-anion products is attributed to the size and bonding variance across the chalcogen series. The degree of ordering varies according to the distinctiveness of the local chemistry at the anion sites and additionally the specific combination of chalcogens employed in the reaction. Additionally, we find that mixed-chalcogen products can adopt phases that are distinct from their single-anion end members, including KCuZrTe₂S (P2₁/m), where an alternate arrangement of polyhedral building blocks maximizes favorable bonding interactions. Density-functional theory calculations corroborate the experimental findings and offer additional insights into the ordering trends. We anticipate that the reverse-engineering approach, which is inspired by the retrosynthetic analyses used in molecular chemistry, will help accelerate the discovery and understanding of heteroanionic phenomena.