Shaun O’Donnell, Ian A. Leahy, Subhendu Jana, Eric A. Gabilondo, P. Shiv Halasyamani, Paul A. Maggard, Rebecca W. Smaha
{"title":"手性三元硫属化合物Eu2SiSe4的磁性和大二次谐波产生响应","authors":"Shaun O’Donnell, Ian A. Leahy, Subhendu Jana, Eric A. Gabilondo, P. Shiv Halasyamani, Paul A. Maggard, Rebecca W. Smaha","doi":"10.1021/acs.chemmater.5c00421","DOIUrl":null,"url":null,"abstract":"Eu(II)-containing chalcogenides are an emerging class of materials that are of great interest due to their high optical activity and intriguing magnetism. Here, we synthesized Eu<sub>2</sub>SiSe<sub>4</sub> as red-colored single crystals and characterized its structure with single-crystal X-ray diffraction, confirming the reported chiral monoclinic <i>P</i>2<sub>1</sub> symmetry at room temperature. The crystal structure of Eu<sub>2</sub>SiSe<sub>4</sub> comprises distorted SiSe<sub>4</sub> tetrahedral units and charge-balancing Eu(II) cations. Here, we develop a two-step solid-state synthesis method for Eu<sub>2</sub>SiSe<sub>4</sub> and compare it to the known boron chalcogenide method. We find the second-harmonic generation (SHG) activity of polycrystalline Eu<sub>2</sub>SiSe<sub>4</sub> to be ∼7 × AgGaS<sub>2</sub>, placing it among the highest-known SHG-active chalcogenides. No symmetry lowering is observed down to 100 K in single-crystal X-ray diffraction, although an anomalous expansion in the <i>b</i>-axis lattice parameter occurs and may be correlated to lattice modes of the SiSe<sub>4</sub> tetrahedra. We investigate the physical properties of Eu<sub>2</sub>SiSe<sub>4</sub> using magnetometry and heat capacity measurements and find a transition to an antiferromagnetic ground state at <i>T</i><sub><i>N</i></sub> ≈ 5.5 K. The low-temperature transition releases less entropy than expected, which may be due to the complex crystal electric field effects of Eu(II).","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"84 1","pages":""},"PeriodicalIF":7.0000,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Magnetic Properties and Large Second-Harmonic Generation Response of a Chiral Ternary Chalcogenide: Eu2SiSe4\",\"authors\":\"Shaun O’Donnell, Ian A. Leahy, Subhendu Jana, Eric A. Gabilondo, P. Shiv Halasyamani, Paul A. Maggard, Rebecca W. Smaha\",\"doi\":\"10.1021/acs.chemmater.5c00421\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Eu(II)-containing chalcogenides are an emerging class of materials that are of great interest due to their high optical activity and intriguing magnetism. Here, we synthesized Eu<sub>2</sub>SiSe<sub>4</sub> as red-colored single crystals and characterized its structure with single-crystal X-ray diffraction, confirming the reported chiral monoclinic <i>P</i>2<sub>1</sub> symmetry at room temperature. The crystal structure of Eu<sub>2</sub>SiSe<sub>4</sub> comprises distorted SiSe<sub>4</sub> tetrahedral units and charge-balancing Eu(II) cations. Here, we develop a two-step solid-state synthesis method for Eu<sub>2</sub>SiSe<sub>4</sub> and compare it to the known boron chalcogenide method. We find the second-harmonic generation (SHG) activity of polycrystalline Eu<sub>2</sub>SiSe<sub>4</sub> to be ∼7 × AgGaS<sub>2</sub>, placing it among the highest-known SHG-active chalcogenides. No symmetry lowering is observed down to 100 K in single-crystal X-ray diffraction, although an anomalous expansion in the <i>b</i>-axis lattice parameter occurs and may be correlated to lattice modes of the SiSe<sub>4</sub> tetrahedra. We investigate the physical properties of Eu<sub>2</sub>SiSe<sub>4</sub> using magnetometry and heat capacity measurements and find a transition to an antiferromagnetic ground state at <i>T</i><sub><i>N</i></sub> ≈ 5.5 K. The low-temperature transition releases less entropy than expected, which may be due to the complex crystal electric field effects of Eu(II).\",\"PeriodicalId\":33,\"journal\":{\"name\":\"Chemistry of Materials\",\"volume\":\"84 1\",\"pages\":\"\"},\"PeriodicalIF\":7.0000,\"publicationDate\":\"2025-07-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry of Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.chemmater.5c00421\",\"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://doi.org/10.1021/acs.chemmater.5c00421","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}
Magnetic Properties and Large Second-Harmonic Generation Response of a Chiral Ternary Chalcogenide: Eu2SiSe4
Eu(II)-containing chalcogenides are an emerging class of materials that are of great interest due to their high optical activity and intriguing magnetism. Here, we synthesized Eu2SiSe4 as red-colored single crystals and characterized its structure with single-crystal X-ray diffraction, confirming the reported chiral monoclinic P21 symmetry at room temperature. The crystal structure of Eu2SiSe4 comprises distorted SiSe4 tetrahedral units and charge-balancing Eu(II) cations. Here, we develop a two-step solid-state synthesis method for Eu2SiSe4 and compare it to the known boron chalcogenide method. We find the second-harmonic generation (SHG) activity of polycrystalline Eu2SiSe4 to be ∼7 × AgGaS2, placing it among the highest-known SHG-active chalcogenides. No symmetry lowering is observed down to 100 K in single-crystal X-ray diffraction, although an anomalous expansion in the b-axis lattice parameter occurs and may be correlated to lattice modes of the SiSe4 tetrahedra. We investigate the physical properties of Eu2SiSe4 using magnetometry and heat capacity measurements and find a transition to an antiferromagnetic ground state at TN ≈ 5.5 K. The low-temperature transition releases less entropy than expected, which may be due to the complex crystal electric field effects of Eu(II).
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.