20.500.12556/DiRROS-22142 Pressure-induced comproportionation in palladium trifluoride Despite its seeming simple stoichiometry, palladium trifluoride (PdF3) is a mixed-valent system better formulated as PdIIPdIVF6. In an attempt to verify whether the application of high pressure (P > 1 GPa) might force this compound to form a genuine palladium(III) fluoride (PdIIIF3), a joint theoretical and experimental study on its properties at large compression was performed. Indeed, hybrid density functional calculations predict the thermodynamic preference for single-valent (comproportionated) polymorphs at pressures exceeding 30 GPa. The ambient-pressure LiSbF6-type polymorph of R3̅ symmetry was experimentally observed to transform into a triclinic P1̅ phase above 42 GPa. While this polymorph is still a mixed-valent compound PdIIPdIVF6, another phase transition, commencing at ∼50 GPa, introduces a monoclinic C2/c phase containing genuine PdIII centers. Both high-pressure polymorphs of palladium trifluoride exhibit novel structure types. Moreover, preliminary data suggest that the C2/c comproportionated structure might host strong one-dimensional antiferromagnetic exchange interactions. palladium fluoride high pressure comproportionation DFT calculations paladijev fluorid visoki tlaki koproporcionacija DFT izračuni true false true Angleški jezik Slovenski jezik Neznano 2025-05-05 13:01:09 2025-05-05 13:01:09 2025-10-24 03:50:36 0000-00-00 00:00:00 2025 0 0 Nasl. z nasl. zaslona; Soavtorji iz Slovenije: Klemen Motaln, Mirela Dragomir, Matic Lozinšek; Opis vira z dne 5. 5. 2025; str. A-I iss. Vol. 64 [in press] 2025 0000-00-00 Zaloznikova Objavljeno NiDoloceno 2025-01-30 2025-04-17 2025-04-30 546 1520-510X 10.1021/acs.inorgchem.5c00465 234718979 https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00465 1 411d96d4-29a0-11f0-963a-001a4af901a5 https://dirros.openscience.si/Dokument.php?lang=slv&id=32028 RAZ_Olszewska_Sylwia_2025.pdf RAZ_Olszewska_Sylwia_2025.pdf The data supporting the findings of this study are available on the Repository for Open Data server (https://repod.icm.edu.pl/) under the DOI number: 10.18150/SG2SSB. 1 635C2084E5B59474EDF6B59D4A039942 372c9d25ee8695916d08e9a667ead94541117fa3b9877319b3ba2857f84d4f54 f5a66ee4-29a1-11f0-963a-001a4af901a5 https://dirros.openscience.si/Dokument.php?lang=slv&id=32029 Institut Jožef Stefan 0 0 0