{"title":"Smaller rare-earth cation and mixed valent Mn incorporation as a dual strategy to enhance ferrimagnetic ordering temperatures in A-site ordered quadruple perovskites, LnCu3Mn1+xTi3−xO12 (Ln = La, Nd; x = 0, 0.3)","authors":"Lalit Kumar, Sujan Sen, Tapas Kumar Mandal","doi":"10.1039/d4dt01859a","DOIUrl":null,"url":null,"abstract":"High-T<small><sub>C</sub></small> ferro-/ferrimagnetic quadruple perovskites constitute an important class of oxides that has garnered a lot of research attention in recent times, but, their synthesis is commonly achieved under high-pressure condition. Thus, development of high-T<small><sub>C</sub></small> quadruple perovskites that can be synthesized under ambient pressure can be a key to the above problem. Herein, we report ambient pressure synthesis of a series of new A-site ordered quadruple perovskites, LnCu3Mn1+xTi3-xO12 (Ln = La, Nd; x = 0, 0.3), by coupled aliovalent-cation manipulation in CaCu3Ti4O12. The effect of smaller lanthanide Nd incorporation in place of La has ben investigated. Further, 30% mixed valency of Mn per Mn3+ has been introduced in place of Ti4+ following similar strategies adopted to achieve giant magnetoresistive manganites La0.7A0.3MnO3 (A = Ca, Sr, Ba) from LaMnO3. Mn is present in 3+ state for x = 0 and in a mixed valent state (3+ and 4+) for x = 0.3, whereas Cu exist in 2+ state in all the compounds. While LaCu3MnTi3O12 and LaCu3Mn1.3Ti2.7O12 show onset of ferrimagnetic order at ~ 60 and 110 K, respectively, the corresponding Nd analogs, NdCu3MnTi3O12 and NdCu3Mn1.3Ti2.7O12 exhibit enhanced T<small><sub>C</sub></small>’s of ~ 80 and 140 K. The work reveals an effective strategy of mixed-valent Mn incorporation in the B-sublattice and smaller rare-earth incorporation to achieve higher ferrimagnetic ordering temperatures in the quadruple perovskites.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4dt01859a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
High-TC ferro-/ferrimagnetic quadruple perovskites constitute an important class of oxides that has garnered a lot of research attention in recent times, but, their synthesis is commonly achieved under high-pressure condition. Thus, development of high-TC quadruple perovskites that can be synthesized under ambient pressure can be a key to the above problem. Herein, we report ambient pressure synthesis of a series of new A-site ordered quadruple perovskites, LnCu3Mn1+xTi3-xO12 (Ln = La, Nd; x = 0, 0.3), by coupled aliovalent-cation manipulation in CaCu3Ti4O12. The effect of smaller lanthanide Nd incorporation in place of La has ben investigated. Further, 30% mixed valency of Mn per Mn3+ has been introduced in place of Ti4+ following similar strategies adopted to achieve giant magnetoresistive manganites La0.7A0.3MnO3 (A = Ca, Sr, Ba) from LaMnO3. Mn is present in 3+ state for x = 0 and in a mixed valent state (3+ and 4+) for x = 0.3, whereas Cu exist in 2+ state in all the compounds. While LaCu3MnTi3O12 and LaCu3Mn1.3Ti2.7O12 show onset of ferrimagnetic order at ~ 60 and 110 K, respectively, the corresponding Nd analogs, NdCu3MnTi3O12 and NdCu3Mn1.3Ti2.7O12 exhibit enhanced TC’s of ~ 80 and 140 K. The work reveals an effective strategy of mixed-valent Mn incorporation in the B-sublattice and smaller rare-earth incorporation to achieve higher ferrimagnetic ordering temperatures in the quadruple perovskites.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.