| Title: | Pressure-induced comproportionation in palladium trifluoride |
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| Authors: | ID Olszewska, Sylwia (Author)
ID Pillai, Sharad Babu (Author)
ID Upadhyay, Deepak (Author)
ID Zdun, Kinga (Author)
ID Drapała, Jakub (Author)
ID Motaln, Klemen, Institut "Jožef Stefan" (Author)
ID Dragomir, Mirela, Institut "Jožef Stefan" (Author)
ID Lozinšek, Matic, Institut "Jožef Stefan" (Author)
ID Kurzydłowski, Dominik (Author) |
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| Files: |  URL - Source URL, visit https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00465
 PDF - Presentation file, download (3,01 MB)
MD5: 635C2084E5B59474EDF6B59D4A039942
Description: 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.
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| Language: | English |
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| Typology: | 1.01 - Original Scientific Article |
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| Organization: |  IJS - Jožef Stefan Institute
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| Abstract: | 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. |
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| Keywords: | palladium fluoride, high pressure, comproportionation, DFT calculations |
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| Publication status: | Published |
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| Publication version: | Version of Record |
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| Submitted for review: | 30.01.2025 |
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| Article acceptance date: | 17.04.2025 |
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| Publication date: | 30.04.2025 |
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| Year of publishing: | 2025 |
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| Number of pages: | str. A-I |
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| Numbering: | Vol. 64, iss. |
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| PID: | 20.500.12556/DiRROS-22142  |
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| UDC: | 546 |
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| ISSN on article: | 1520-510X |
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| DOI: | 10.1021/acs.inorgchem.5c00465 |
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| COBISS.SI-ID: | 234718979 |
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| Note: | Nasl. z nasl. zaslona;
Soavtorji iz Slovenije: Klemen Motaln, Mirela Dragomir, Matic Lozinšek;
Opis vira z dne 5. 5. 2025;
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| Publication date in DiRROS: | 05.05.2025 |
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| Views: | 809 |
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| Downloads: | 991 |
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