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Issue 5, 2019
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High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies

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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 Fm[3 with combining macron]m to R[3 with 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.

Graphical abstract: High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies

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Article information


Submitted
09 Nov 2018
Accepted
04 Dec 2018
First published
04 Dec 2018

Dalton Trans., 2019,48, 1647-1655
Article type
Paper

High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies

H. L. B. Boström, I. E. Collings, A. B. Cairns, C. P. Romao and A. L. Goodwin, Dalton Trans., 2019, 48, 1647
DOI: 10.1039/C8DT04463E

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