Makoto Iihoshi, Masato Goto and Yuichi Shimakawa*,
{"title":"LnBaFe2O6 （Ln = Pr，Sm）中混合和异常高价的 Fe3.5+ 通过连续电荷转换产生的电荷比例失调状态的稳定性","authors":"Makoto Iihoshi, Masato Goto and Yuichi Shimakawa*, ","doi":"10.1021/acs.chemmater.4c00578","DOIUrl":null,"url":null,"abstract":"<p >A-site layer-ordered double perovskites <i>Ln</i>BaFe<sub>2</sub>O<sub>6</sub> (<i>Ln</i> = Pr, Sm) were synthesized by topotactic ozone oxidation, and their successive phase transition behaviors were investigated. The results of differential scanning calorimetry, X-ray powder diffraction, Mössbauer spectroscopy, and magnetization measurements suggested that both compounds exhibited successive charge transitions accompanied by complicated changes in physical properties, involving the charge, lattice, and spin degrees of freedom. For SmBaFe<sub>2</sub>O<sub>6</sub>, the first-order structural and magnetic transition related to the first charge disproportionation transition (2Fe<sup>3.5+</sup> → Fe<sup>3+</sup> + Fe<sup>4+</sup>) occurred at a higher temperature than that of PrBaFe<sub>2</sub>O<sub>6</sub>, while the second-order magnetic transition, which was induced by the second charge disproportionation (Fe<sup>4+</sup> → 0.5Fe<sup>3+</sup> + 0.5Fe<sup>5+</sup>) was observed at a lower temperature. The obtained results suggest that the metastable charge-disproportionated state (Fe<sup>3+</sup> + Fe<sup>4+</sup>) of <i>Ln</i>BaFe<sub>2</sub>O<sub>6</sub> is more stabilized when the lanthanoid ion at the A-site is smaller.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2000,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Stabilities of Charge Disproportionated States by Successive Charge Transitions of Mixed and Unusually High Valence Fe3.5+ in LnBaFe2O6 (Ln = Pr, Sm)\",\"authors\":\"Makoto Iihoshi, Masato Goto and Yuichi Shimakawa*, \",\"doi\":\"10.1021/acs.chemmater.4c00578\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A-site layer-ordered double perovskites <i>Ln</i>BaFe<sub>2</sub>O<sub>6</sub> (<i>Ln</i> = Pr, Sm) were synthesized by topotactic ozone oxidation, and their successive phase transition behaviors were investigated. The results of differential scanning calorimetry, X-ray powder diffraction, Mössbauer spectroscopy, and magnetization measurements suggested that both compounds exhibited successive charge transitions accompanied by complicated changes in physical properties, involving the charge, lattice, and spin degrees of freedom. For SmBaFe<sub>2</sub>O<sub>6</sub>, the first-order structural and magnetic transition related to the first charge disproportionation transition (2Fe<sup>3.5+</sup> → Fe<sup>3+</sup> + Fe<sup>4+</sup>) occurred at a higher temperature than that of PrBaFe<sub>2</sub>O<sub>6</sub>, while the second-order magnetic transition, which was induced by the second charge disproportionation (Fe<sup>4+</sup> → 0.5Fe<sup>3+</sup> + 0.5Fe<sup>5+</sup>) was observed at a lower temperature. The obtained results suggest that the metastable charge-disproportionated state (Fe<sup>3+</sup> + Fe<sup>4+</sup>) of <i>Ln</i>BaFe<sub>2</sub>O<sub>6</sub> is more stabilized when the lanthanoid ion at the A-site is smaller.</p>\",\"PeriodicalId\":33,\"journal\":{\"name\":\"Chemistry of Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":7.2000,\"publicationDate\":\"2024-06-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry of Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.chemmater.4c00578\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.chemmater.4c00578","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Stabilities of Charge Disproportionated States by Successive Charge Transitions of Mixed and Unusually High Valence Fe3.5+ in LnBaFe2O6 (Ln = Pr, Sm)
A-site layer-ordered double perovskites LnBaFe2O6 (Ln = Pr, Sm) were synthesized by topotactic ozone oxidation, and their successive phase transition behaviors were investigated. The results of differential scanning calorimetry, X-ray powder diffraction, Mössbauer spectroscopy, and magnetization measurements suggested that both compounds exhibited successive charge transitions accompanied by complicated changes in physical properties, involving the charge, lattice, and spin degrees of freedom. For SmBaFe2O6, the first-order structural and magnetic transition related to the first charge disproportionation transition (2Fe3.5+ → Fe3+ + Fe4+) occurred at a higher temperature than that of PrBaFe2O6, while the second-order magnetic transition, which was induced by the second charge disproportionation (Fe4+ → 0.5Fe3+ + 0.5Fe5+) was observed at a lower temperature. The obtained results suggest that the metastable charge-disproportionated state (Fe3+ + Fe4+) of LnBaFe2O6 is more stabilized when the lanthanoid ion at the A-site is smaller.
期刊介绍：
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.
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