High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies
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...
| मुख्य लेखकों: | , , , , |
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| स्वरूप: | Journal article |
| भाषा: | English |
| प्रकाशित: |
Royal Society of Chemistry
2018
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| सारांश: | 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. |
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