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Synthesis, Crystal Structure, and Properties of La4Zn7P10 and La4Mg1.5Zn8.5P12

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    Synthesis, Crystal Structure, and Properties of La4Zn7P10 and La4Mg1.5Zn8.5P12
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    Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, United States
    *E-mail: [email protected]
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 2, 783–790
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    https://doi.org/10.1021/acs.inorgchem.6b02216
    Published December 22, 2016
    Copyright © 2016 American Chemical Society
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    Abstract

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    Two new zinc phosphides, La4Zn7P10 and La4Mg1.5Zn8.5P12, were synthesized via transport reactions, and their crystal structures were determined by single crystal X-ray diffraction. La4Zn7P10 and La4Mg1.5Zn8.5P12 are built from three-dimensional Zn–P and Zn–Mg–P anionic frameworks that encapsulate lanthanum atoms. The anionic framework of La4Zn7P10 is constructed from one-dimensional Zn4P6, Zn2P4, and ZnP4 chains. The Zn4P6 chains are also the main building units in La4Mg1.5Zn8.5P12. In La4Zn7P10, the displacement of a zinc atom from the origin of the unit cell causes the Zn4 position to split into two equivalent atomic sites, each with 50% occupancy. The splitting of the atomic position substantially modifies the electronic properties, as suggested by theoretical calculations. The necessity of splitting can be overcome by replacement of zinc with magnesium in La4Mg1.5Zn8.5P12. Investigation of the transport properties of a densified polycrystalline sample of La4Zn7P10 demonstrates that it is an n-type semiconductor with a small bandgap of ∼0.04 eV at 300 K. La4Zn7P10 also exhibits low thermal conductivity, 1.3 Wm–1 K–1 at 300 K, which mainly originates from the lattice thermal conductivity. La4Zn7P10 is stable in a sealed evacuated ampule up to 1123 K as revealed by differential scanning calorimetry.

    Copyright © 2016 American Chemical Society

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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.inorgchem.6b02216.

    • Calculated and experimental powder X-ray diffraction patterns, EDS results of La4Zn7P10 and La4Mg1.5Zn8.5P12, differential scanning calorimetry plot of La4Zn7P10, tables with refined atomic coordinates, displacement parameters, and selected interatomic distances for La4Zn7P10 and La4Mg1.5Zn8.5P12, figures for the coordination of the split phosphorus positions, and additional ELF and COHP figures. (PDF)

    • Crystallographic information file for La4Zn7P10 (CIF)

    • Crystallographic information file for La4Mg1.5Zn8.5P12 (CIF)

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 2, 783–790
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.6b02216
    Published December 22, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

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