Issue 9, 2024

The pressure response of Jahn–Teller-distorted Prussian blue analogues

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.

Graphical abstract: The pressure response of Jahn–Teller-distorted Prussian blue analogues

Supplementary files

Article information

Article type
Edge Article
Submitted
23 12 2023
Accepted
19 1 2024
First published
23 1 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 3155-3164

The pressure response of Jahn–Teller-distorted Prussian blue analogues

H. L. B. Boström, A. B. Cairns, M. Chen, D. Daisenberger, C. J. Ridley and N. P. Funnell, Chem. Sci., 2024, 15, 3155 DOI: 10.1039/D3SC06912E

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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