Structural modification of the cation-ordered Ruddlesden-Popper phase YSr2Mn2O7 by cation exchange and anion insertion
Calcium-for-strontium cation substitution of the a(-)b(0)c(0)/b(0)a(-)c(0)-distorted, cation-ordered, n = 2 Ruddlesden-Popper phase, YSr2Mn2O7, leads to separation into two phases, which both retain an a(-)b(0)c(0)/b(0)a(-)c(0)-distorted framework and have the same stoichiometry but exhibit differen...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
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American Chemical Society
2017
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| _version_ | 1826302497415757824 |
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| author | Zhang, R Gibbs, A Zhang, W Halasyamani, P Hayward, M |
| author_facet | Zhang, R Gibbs, A Zhang, W Halasyamani, P Hayward, M |
| author_sort | Zhang, R |
| collection | OXFORD |
| description | Calcium-for-strontium cation substitution of the a(-)b(0)c(0)/b(0)a(-)c(0)-distorted, cation-ordered, n = 2 Ruddlesden-Popper phase, YSr2Mn2O7, leads to separation into two phases, which both retain an a(-)b(0)c(0)/b(0)a(-)c(0)-distorted framework and have the same stoichiometry but exhibit different degrees of Y/Sr/Ca cation order. Increasing the calcium concentration to form YSr0.5Ca1.5Mn2O7 leads to a change in the cooperative tilting on the MnO6 units to a novel a(-)b(-)c(-)/b(-)a(-)c(-) arrangement described in space group P21/n11. Low-temperature, topochemical fluorination of YSr2Mn2O7 yields YSr2Mn2O5.5F3.5. In contrast to many other fluorinated n = 2 Ruddlesden-Popper oxide phases, YSr2Mn2O5.5F3.5 retains the a(-)b(0)c(0)/b(0)a(-)c(0) lattice distortion and P42/mnm space group symmetry of the parent oxide phase. The resilience of the a(-)b(0)c(0)/b(0)a(-)c(0)-distorted framework of YSr2Mn2O7 to resist symmetry-changing deformations upon both cation substitution and anion insertion/exchange is discussed on the basis the A-site cation order of the lattice and the large change in the ionic radius of manganese upon oxidation from Mn(3+) to Mn(4+). The structure property relations observed in the Y-Sr-Ca-Mn-O-F system provide insight into assisting in the synthesis of n = 2 Ruddlesden-Popper phases, which adopt cooperative structural distortions that break the inversion symmetry of the extended lattice and therefore act as a route for the preparation of ferroelectric and multiferroic materials. |
| first_indexed | 2024-03-07T05:48:26Z |
| format | Journal article |
| id | oxford-uuid:e801d7fc-c20f-494b-9023-934a4ff7b2e6 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T05:48:26Z |
| publishDate | 2017 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:e801d7fc-c20f-494b-9023-934a4ff7b2e62022-03-27T10:43:28ZStructural modification of the cation-ordered Ruddlesden-Popper phase YSr2Mn2O7 by cation exchange and anion insertionJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:e801d7fc-c20f-494b-9023-934a4ff7b2e6EnglishSymplectic Elements at OxfordAmerican Chemical Society2017Zhang, RGibbs, AZhang, WHalasyamani, PHayward, MCalcium-for-strontium cation substitution of the a(-)b(0)c(0)/b(0)a(-)c(0)-distorted, cation-ordered, n = 2 Ruddlesden-Popper phase, YSr2Mn2O7, leads to separation into two phases, which both retain an a(-)b(0)c(0)/b(0)a(-)c(0)-distorted framework and have the same stoichiometry but exhibit different degrees of Y/Sr/Ca cation order. Increasing the calcium concentration to form YSr0.5Ca1.5Mn2O7 leads to a change in the cooperative tilting on the MnO6 units to a novel a(-)b(-)c(-)/b(-)a(-)c(-) arrangement described in space group P21/n11. Low-temperature, topochemical fluorination of YSr2Mn2O7 yields YSr2Mn2O5.5F3.5. In contrast to many other fluorinated n = 2 Ruddlesden-Popper oxide phases, YSr2Mn2O5.5F3.5 retains the a(-)b(0)c(0)/b(0)a(-)c(0) lattice distortion and P42/mnm space group symmetry of the parent oxide phase. The resilience of the a(-)b(0)c(0)/b(0)a(-)c(0)-distorted framework of YSr2Mn2O7 to resist symmetry-changing deformations upon both cation substitution and anion insertion/exchange is discussed on the basis the A-site cation order of the lattice and the large change in the ionic radius of manganese upon oxidation from Mn(3+) to Mn(4+). The structure property relations observed in the Y-Sr-Ca-Mn-O-F system provide insight into assisting in the synthesis of n = 2 Ruddlesden-Popper phases, which adopt cooperative structural distortions that break the inversion symmetry of the extended lattice and therefore act as a route for the preparation of ferroelectric and multiferroic materials. |
| spellingShingle | Zhang, R Gibbs, A Zhang, W Halasyamani, P Hayward, M Structural modification of the cation-ordered Ruddlesden-Popper phase YSr2Mn2O7 by cation exchange and anion insertion |
| title | Structural modification of the cation-ordered Ruddlesden-Popper phase YSr2Mn2O7 by cation exchange and anion insertion |
| title_full | Structural modification of the cation-ordered Ruddlesden-Popper phase YSr2Mn2O7 by cation exchange and anion insertion |
| title_fullStr | Structural modification of the cation-ordered Ruddlesden-Popper phase YSr2Mn2O7 by cation exchange and anion insertion |
| title_full_unstemmed | Structural modification of the cation-ordered Ruddlesden-Popper phase YSr2Mn2O7 by cation exchange and anion insertion |
| title_short | Structural modification of the cation-ordered Ruddlesden-Popper phase YSr2Mn2O7 by cation exchange and anion insertion |
| title_sort | structural modification of the cation ordered ruddlesden popper phase ysr2mn2o7 by cation exchange and anion insertion |
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