Pressure-induced comproportionation in palladium trifluorideOlszewska, Sylwia (Avtor) Pillai, Sharad Babu (Avtor) Upadhyay, Deepak (Avtor) Zdun, Kinga (Avtor) Drapała, Jakub (Avtor) Motaln, Klemen (Avtor) Dragomir, Mirela (Avtor) Lozinšek, Matic (Avtor) Kurzydłowski, Dominik (Avtor) palladium fluoridehigh pressurecomproportionationDFT calculationsDespite 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.20252025-05-05 13:01:09Neznano22142UDK: 546ISSN pri članku: 1520-510XDOI: 10.1021/acs.inorgchem.5c00465COBISS_ID: 234718979sl