High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies
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Accepted version
Author(s)
Boström, Hanna LB
Collings, Ines E
Cairns, Andrew B
Romao, Carl P
Goodwin, Andrew L
Type
Journal Article
Abstract
We report a high-pressure crystallographic study of four hydrated Prussian blue analogues: M[Pt(CN)6] and M[Co(CN)6]0.67 (M = Mn2+, Cu2+) in the range 0-3 GPa. Mn[Co(CN)6]0.67 was studied by single-crystal X-ray diffraction, whereas the other systems were only available in polycrystalline form. The Mn-containing compounds undergo pressure-induced phase transitions from Fm3[combining macron]m to R3[combining macron] at ∼1.0-1.5 GPa driven by cooperative tilting of the octahedral units. No phase transition was found for the orbitally disordered Cu[Co(CN)6]0.67 up to 3 GPa. Mn[Co(CN)6]0.67 is significantly softer than the other samples, with a bulk modulus of ∼14 GPa compared to ∼35 GPa of the powdered samples. The discrepant pressure responses are discussed in terms of the presence of structural defects, Jahn-Teller distortions, and hydration. The implications for the development of polar systems are reviewed based upon our high-pressure study.
Date Issued
2019-02-07
Date Acceptance
2018-12-04
Citation
Dalton Transactions, 2019, 48, pp.1647-1655
ISSN
1477-9234
Publisher
Royal Society of Chemistry
Start Page
1647
End Page
1655
Journal / Book Title
Dalton Transactions
Volume
48
Copyright Statement
© 2018 The Royal Society of Chemistry.
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/30548036
Subjects
0302 Inorganic Chemistry
0399 Other Chemical Sciences
Inorganic & Nuclear Chemistry
Publication Status
Published
Coverage Spatial
England
Date Publish Online
2018-12-04