Carla M. Uribe-Rincón , Kowsik Ghosh , Thomas Frederichs , Thorsten M. Gesing , M. Mangir Murshed
{"title":"Synthesis of schafarzikite-type (PbBi)MnO4: Structural, spectroscopic, magnetic and thermogravimetric properties","authors":"Carla M. Uribe-Rincón , Kowsik Ghosh , Thomas Frederichs , Thorsten M. Gesing , M. Mangir Murshed","doi":"10.1016/j.jssc.2025.125215","DOIUrl":null,"url":null,"abstract":"<div><div>Stereochemically active lone electron pairs (LEPs) draw research attention in designing materials for given crystal-physico-chemical properties. While the 5<em>s</em><sup>2</sup> LEP-containing schafarzikite (FeSb<sub>2</sub>O<sub>4</sub>) exhibits interesting properties, we report a new compound (PbBi)MnO<sub>4</sub> which is isostructural to schafarzikites, where the stereochemical activity of 6<em>s</em><sup>2</sup>-LEP is served by both Pb<sup>2+</sup> and Bi<sup>3+</sup> cations located in a single crystallographic site. The phase pure sample has been prepared in a sealed quartz tube with a low pressure of about 1 Pa at 923 K. Both X-ray and neutron power diffraction data Rietveld refinements confirm (PbBi)MnO<sub>4</sub> to be crystallized in the space group <em>P</em>4<sub>2</sub>/<em>mbc</em>. The Wang-Liebau eccentricity parameter that measures the strength of the stereochemical activity of the LEPs of the associated Pb<sup>2+</sup> and Bi<sup>3+</sup> cations was found to be 3.41(2)⋅10<sup>−5</sup>. Temperature dependent DC magnetic susceptibility suggests that (PbBi)MnO<sub>4</sub> is antiferromagnetic at <em>T</em><sub><em>N</em></sub> of 43(1) K, and the magnetic structure follows a G-type configuration determined by neutron diffraction at low-temperature. Thermogravimetric analysis demonstrates the thermal stability of the tetragonal phase. The lattice thermal expansion has been modeled for the low-temperature neutron data using a single Debye term, leading to a Debye temperature of 378(20) K. Temperature-dependent changes of some selective Raman frequencies are mainly dominated by the quasiharmonic effects over the isochoric anharmonicity below room temperature.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125215"},"PeriodicalIF":3.2000,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Solid State Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022459625000386","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
Stereochemically active lone electron pairs (LEPs) draw research attention in designing materials for given crystal-physico-chemical properties. While the 5s2 LEP-containing schafarzikite (FeSb2O4) exhibits interesting properties, we report a new compound (PbBi)MnO4 which is isostructural to schafarzikites, where the stereochemical activity of 6s2-LEP is served by both Pb2+ and Bi3+ cations located in a single crystallographic site. The phase pure sample has been prepared in a sealed quartz tube with a low pressure of about 1 Pa at 923 K. Both X-ray and neutron power diffraction data Rietveld refinements confirm (PbBi)MnO4 to be crystallized in the space group P42/mbc. The Wang-Liebau eccentricity parameter that measures the strength of the stereochemical activity of the LEPs of the associated Pb2+ and Bi3+ cations was found to be 3.41(2)⋅10−5. Temperature dependent DC magnetic susceptibility suggests that (PbBi)MnO4 is antiferromagnetic at TN of 43(1) K, and the magnetic structure follows a G-type configuration determined by neutron diffraction at low-temperature. Thermogravimetric analysis demonstrates the thermal stability of the tetragonal phase. The lattice thermal expansion has been modeled for the low-temperature neutron data using a single Debye term, leading to a Debye temperature of 378(20) K. Temperature-dependent changes of some selective Raman frequencies are mainly dominated by the quasiharmonic effects over the isochoric anharmonicity below room temperature.
期刊介绍:
Covering major developments in the field of solid state chemistry and related areas such as ceramics and amorphous materials, the Journal of Solid State Chemistry features studies of chemical, structural, thermodynamic, electronic, magnetic, and optical properties and processes in solids.