SCHEDULED MAINTENANCE
The pressure response of Jahn–Teller-distorted Prussian blue analogues†
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Andrew B.
Cairns,
de
Muzi
Chen,
de
Christopher J.
Ridley
g
and
Nicholas P.
Funnell
g
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.
- This article is part of the themed collections: #MyFirstChemSci 2024 and 2024 Chemical Science HOT Article Collection
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