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...
| Main Authors: | , , , , |
|---|---|
| Format: | Journal article |
| Language: | English |
| Published: |
Royal Society of Chemistry
2018
|
| _version_ | 1826279481352912896 |
|---|---|
| author | Boström, HLB Collings, IE Cairns, AB Romao, CP Goodwin, AL |
| author_facet | Boström, HLB Collings, IE Cairns, AB Romao, CP Goodwin, AL |
| author_sort | Boström, HLB |
| collection | OXFORD |
| description | 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. |
| first_indexed | 2024-03-06T23:59:22Z |
| format | Journal article |
| id | oxford-uuid:756121d1-ddc2-459a-b670-a9bdd91daf74 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:59:22Z |
| publishDate | 2018 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | oxford-uuid:756121d1-ddc2-459a-b670-a9bdd91daf742022-03-26T20:09:03ZHigh-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacanciesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:756121d1-ddc2-459a-b670-a9bdd91daf74EnglishSymplectic Elements at OxfordRoyal Society of Chemistry2018Boström, HLBCollings, IECairns, ABRomao, CPGoodwin, ALWe 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. |
| spellingShingle | Boström, HLB Collings, IE Cairns, AB Romao, CP Goodwin, AL High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies |
| title | High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies |
| title_full | High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies |
| title_fullStr | High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies |
| title_full_unstemmed | High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies |
| title_short | High-pressure behaviour of Prussian blue analogues: interplay of hydration, Jahn-Teller distortions and vacancies |
| title_sort | high pressure behaviour of prussian blue analogues interplay of hydration jahn teller distortions and vacancies |
| work_keys_str_mv | AT bostromhlb highpressurebehaviourofprussianblueanaloguesinterplayofhydrationjahntellerdistortionsandvacancies AT collingsie highpressurebehaviourofprussianblueanaloguesinterplayofhydrationjahntellerdistortionsandvacancies AT cairnsab highpressurebehaviourofprussianblueanaloguesinterplayofhydrationjahntellerdistortionsandvacancies AT romaocp highpressurebehaviourofprussianblueanaloguesinterplayofhydrationjahntellerdistortionsandvacancies AT goodwinal highpressurebehaviourofprussianblueanaloguesinterplayofhydrationjahntellerdistortionsandvacancies |