Solana Madruga, ElenaMentré, OlivierTsirlin, Alexander A.Huvé, MarielleKhalyavin, DmitryRitter, ClemensArévalo López, Ángel Moisés2026-03-252026-03-252024-03-06Elena Solana-Madruga, Olivier Mentré, Alexander A. Tsirlin, Marielle Huvé, Dmitry Khalyavin, Clemens Ritter, and Angel Moisés Arévalo-López. Adv. Sci. 2024, 11, 2307766. DOI: 10.1002/advs.20230776610.1002/advs.202307766https://hdl.handle.net/20.500.14352/134287Materials properties are determined by their compositions and structures. In ABO3 oxides different cation orderings lead to mainly perovskite- or corundum like derivatives with exciting physical properties. Sometimes, a material can be stabilized in more than one structural modification, providing a unique opportunity to explore structure-properties relationship. Here, CoVO3 obtained in both ilmenite-(CoVO3-I) and LiNbO3-type (CoVO3-II) polymorphs at moderate (8–12 GPa) and high pressures (22 GPa), respectively are presented. Their distinctive cation distributions affect drastically the magnetic properties as CoVO3-II shows a cluster-glass behavior while CoVO3-I hosts a honeycomb zigzag magnetic structure in the cobalt network. First principles calculations show that the influence of vanadium is crucial for CoVO3-I, although it is previously considered as non-magnetic in a dimerized spin-singlet state. Contrarily, CoVO3-II shows two independent interpenetrating antiferromagnetic Co- and ferromagnetic V-hcp sublattices, which intrinsically frustrate any possible magnetic order. CoVO3-II is also remarkable as the first oxide crystallizing with the LiNbO3-type structure where both metals contain free d electrons. CoVO3 polymorphs pinpoint therefore as well to a much broader phase field of high-pressure A-site Cobaltites.engAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/journal articlehttps://doi.org/10.1002/advs.202307766Digital Object Identifier (DOI)https://advanced.onlinelibrary.wiley.com/doi/full/10.1002/advs.202307766open access546Cation orderingHigh-pressure phasesMagnetismCiencias2303 Química Inorgánica