The pressure response of Jahn-Teller-distorted Prussian blue analogues
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Published version
Author(s)
Type
Journal Article
Abstract
Jahn-Teller (JT) distorted CuII-containing compounds often display interesting structural and functional behaviour upon compression. We use high-pressure X-ray and neutron diffraction to investigate four JT-distorted Prussian blue analogues: Cu[Co(CN)6]0.67, CuPt(CN)6, and ACuCo(CN)6 (A = Rb, Cs), where the first two were studied in both their hydrated and dehydrated forms. All compounds are less compressible than the JT-inactive MnII-based counterparts, indicating a coupling between the electronic and mechanical properties. The effect is particularly strong for Cu[Co(CN)6]0.67, where the local JT distortions are uncorrelated (so-called orbital disorder). This sample amorphises at 0.5 GPa when dehydrated. CuPt(CN)6 behaves similarly to the MnII-analogues, with phase transitions at around 1 GPa and low sensitivity to water. For ACuCo(CN)6, the JT distortions reduce the propensity for phase transitions, although RbCuCo(CN)6 transitions to a new phase (P2/m) around 3 GPa. Our results have a bearing on both the topical Prussian blue analogues and the wider field of flexible frameworks.
Date Issued
2024-03-07
Date Acceptance
2024-01-19
Citation
Chemical Science, 2024, 15 (9), pp.3155-3164
ISSN
2041-6520
Publisher
The Royal Society of Chemistry
Start Page
3155
End Page
3164
Journal / Book Title
Chemical Science
Volume
15
Issue
9
Copyright Statement
© 2024 The Author(s). Published by the Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
License URL
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/38425511
PII: d3sc06912e
Publication Status
Published
Coverage Spatial
England
Date Publish Online
2024-01-23