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

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 poly-crystalline 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.

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Publication details

The article was received on 09 Nov 2018, accepted on 04 Dec 2018 and first published on 04 Dec 2018


Article type: Paper
DOI: 10.1039/C8DT04463E
Citation: Dalton Trans., 2018, Accepted Manuscript
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    High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies

    H. Boström, I. Collings, A. B. Cairns, C. P. Romao and A. Goodwin, Dalton Trans., 2018, Accepted Manuscript , DOI: 10.1039/C8DT04463E

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