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Eu11Zn4Sn2As12: A Ferromagnetic Zintl Semiconductor with a Layered Structure Featuring Extended Zn4As6 Sheets and Ethane-like Sn2As6 Units

  • Kasey P. Devlin
    Kasey P. Devlin
    Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, United States
  • Nasrin Kazem
    Nasrin Kazem
    Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, United States
    More by Nasrin Kazem
  • Julia V. Zaikina
    Julia V. Zaikina
    Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, United States
  • Joya A. Cooley
    Joya A. Cooley
    Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, United States
  • Jackson R. Badger
    Jackson R. Badger
    Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, United States
  • James C. Fettinger
    James C. Fettinger
    Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, United States
  • Valentin Taufour
    Valentin Taufour
    Department of Physics, University of California, One Shields Avenue, Davis, California 95616, United States
  • , and 
  • Susan M. Kauzlarich*
    Susan M. Kauzlarich
    Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, United States
    *E-mail: [email protected]
Cite this: Chem. Mater. 2018, 30, 20, 7067–7076
Publication Date (Web):September 21, 2018
https://doi.org/10.1021/acs.chemmater.8b02749
Copyright © 2018 American Chemical Society

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    Abstract

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    We report the synthesis, structure, and magnetic properties of a new Zintl phase and structure type, Eu11Zn4Sn2As12. The structure and composition of this phase have been established by single-crystal X-ray diffraction and electron microprobe analysis. Eu11Zn4Sn2As12 crystallizes in monoclinic space group C2/c (No. 15) with the following lattice parameters: a = 7.5679(4) Å, b = 13.0883(6) Å, c = 31.305(2) Å, and β = 94.8444(7)° [R1 = 0.0398; wR2 = 0.0633 (all data)]. The anisotropic structural features staggered ethane-like [Sn2As6]12– units and infinite 2[Zn2As3]5– sheets extended in the a–b plane. Eu cations fill the space between these anionic motifs. Temperature-dependent magnetic properties and magnetoresistance of this Zintl phase have been studied, and the electronic structure and chemical bonding were elucidated using first-principles quantum chemical calculations (TB-LMTO-ASA). Quantum chemical calculations show that the ethane-like units can be considered as consisting of covalent single bonds; however, the 2[Zn2As3]5– sheets are best described with delocalized bonding and there is evidence of Eu–As interactions. Temperature-dependent magnetization and transport properties between 2 and 300 K show a ferromagnetic transition at 15 K, a band gap of 0.04 eV, and negative colossal magnetoresistance.

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.8b02749.

    • Crystal data, structure refinement, atomic coordinates, and equivalent isotropic displacement parameters for Eu11Zn4Sn2As12; band structure diagram for Eu11Zn4Sn2As12; 2D slices and three-dimensional isosurfaces of the electron localization function (η) for Eu layers Ai and Aii; and magnetoresistance data from 120 to 300 K (PDF)

    • Crystallographic information for Eu11Zn4Sn2As12 (CIF)

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    Cited By

    This article is cited by 12 publications.

    1. Ashlee K. Hauble, Michael Y. Toriyama, Stephan Bartling, Ali M. Abdel-Mageed, G. Jeffrey Snyder, Susan M. Kauzlarich. Experiment and Theory in Concert To Unravel the Remarkable Electronic Properties of Na-Doped Eu11Zn4Sn2As12: A Layered Zintl Phase. Chemistry of Materials 2023, 35 (18) , 7719-7729. https://doi.org/10.1021/acs.chemmater.3c01509
    2. Siméon Ponou, Sven Lidin, Anja-Verena Mudring. Optimization of Chemical Bonding through Defect Formation and Ordering─The Case of Mg7Pt4Ge4. Inorganic Chemistry 2023, 62 (22) , 8519-8529. https://doi.org/10.1021/acs.inorgchem.2c04312
    3. Sviatoslav Baranets, Adam Balvanz, Gregory M. Darone, Svilen Bobev. On the Effects of Aliovalent Substitutions in Thermoelectric Zintl Pnictides. Varied Polyanionic Dimensionality and Complex Structural Transformations─The Case of Sr3ZnP3 vs Sr3AlxZn1–xP3. Chemistry of Materials 2022, 34 (9) , 4172-4185. https://doi.org/10.1021/acs.chemmater.2c00527
    4. Kasey P. Devlin, Junjie Zhang, James C. Fettinger, Eun Sang Choi, Ashlee K. Hauble, Valentin Taufour, Raphael P. Hermann, Susan M. Kauzlarich. Deconvoluting the Magnetic Structure of the Commensurately Modulated Quinary Zintl Phase Eu11–xSrxZn4Sn2As12. Inorganic Chemistry 2021, 60 (8) , 5711-5723. https://doi.org/10.1021/acs.inorgchem.0c03769
    5. Yongqi Yang, Guangming Cheng, Joanna Blawat, Duncan H. Moseley, Haozhe Wang, Kasey P. Devlin, Yu Yu, Raphaël P. Hermann, Nan Yao, Rongying Jin, Weiwei Xie. Crystal structure and magnetic properties in semiconducting Eu3−δZn x Sn y As3 with Eu-Eu dimers. Journal of Applied Physics 2022, 132 (4) https://doi.org/10.1063/5.0094013
    6. J. C. Souza, S. M. Thomas, E. D. Bauer, J. D. Thompson, F. Ronning, P. G. Pagliuso, P. F. S. Rosa. Microscopic probe of magnetic polarons in antiferromagnetic Eu 5 In 2 Sb 6 . Physical Review B 2022, 105 (3) https://doi.org/10.1103/PhysRevB.105.035135
    7. Georgiy Akopov, Nethmi W. Hewage, Philip Yox, Gayatri Viswanathan, Shannon J. Lee, Liam P. Hulsebosch, Sarah D. Cady, Alexander L. Paterson, Frédéric A. Perras, Wenqian Xu, Kui Wu, Yaroslav Mudryk, Kirill Kovnir. Synthesis-enabled exploration of chiral and polar multivalent quaternary sulfides. Chemical Science 2021, 12 (44) , 14718-14730. https://doi.org/10.1039/D1SC03685H
    8. Sviatoslav Baranets, Alexander Ovchinnikov, Svilen Bobev. Structural diversity of the Zintl pnictides with rare-earth metals. 2021, 227-324. https://doi.org/10.1016/bs.hpcre.2021.07.001
    9. Priscila Rosa, Yuanfeng Xu, Marein Rahn, Jean Souza, Satya Kushwaha, Larissa Veiga, Alessandro Bombardi, Sean Thomas, Marc Janoschek, Eric Bauer, Mun Chan, Zhijun Wang, Joe Thompson, Neil Harrison, Pascoal Pagliuso, Andrei Bernevig, Filip Ronning. Colossal magnetoresistance in a nonsymmorphic antiferromagnetic insulator. npj Quantum Materials 2020, 5 (1) https://doi.org/10.1038/s41535-020-00256-8
    10. Shibghatullah Muhammady, Adelya S. Erlyanti, Rena Widita, Yudi Darma. Investigation of structural and electronic properties by pnictogen substitution in the layered oxypnictides (LaO)Zn Pn ( Pn = P, As, Sb). International Journal of Quantum Chemistry 2020, 120 (3) https://doi.org/10.1002/qua.26090
    11. Alexander Ovchinnikov, Svilen Bobev. Zintl phases with group 15 elements and the transition metals: A brief overview of pnictides with diverse and complex structures. Journal of Solid State Chemistry 2019, 270 , 346-359. https://doi.org/10.1016/j.jssc.2018.11.029
    12. Alexander Ovchinnikov, Gregory Darone, Bayrammurad Saparov, Svilen Bobev. Exploratory Work in the Quaternary System of Ca–Eu–Cd–Sb: Synthesis, Crystal, and Electronic Structures of New Zintl Solid Solutions. Materials 2018, 11 (11) , 2146. https://doi.org/10.3390/ma11112146

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