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Enclathration of X@La4 Tetrahedra in Channels of Zn–P Frameworks in La3Zn4P6X (X = Cl, Br)

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    Enclathration of X@La4 Tetrahedra in Channels of Zn–P Frameworks in La3Zn4P6X (X = Cl, Br)
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    † †Department of Chemistry and ‡Department of Materials Science, University of California, Davis, One Shields Avenue, Davis, California 95616, United States
    *E-mail: [email protected]
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    Chemistry of Materials

    Cite this: Chem. Mater. 2016, 28, 13, 4741–4750
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    https://doi.org/10.1021/acs.chemmater.6b01752
    Published June 7, 2016
    Copyright © 2016 American Chemical Society
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    Abstract

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    Two new quaternary lanthanum zinc phosphide-halides were synthesized via high-temperature solid-state reactions. Their complex crystal structures were determined by a combination of X-ray diffraction and advanced solid-state 31P NMR spectroscopy. La3Zn4P6Cl and La3Zn4P6.6Br0.8 share a common structural feature: a polyanionic Zn–P framework with large channels hosting complex one-dimensional cations. The cations are built from X@La4 tetrahedral chains with X = Cl (La3Zn4P6Cl) or Br0.8P0.2 (La3Zn4P6.6Br0.8). The X@La4 tetrahedra share two vertices forming one-dimensional chains. To accommodate larger bromine-containing cations the Zn–P framework is rearranged by breaking and forming several Zn–P and P–P bonds. This results in the formation of a unique [P3]3– cycle, which is isoelectronic to cyclopropane. Analysis of the electron localization and orbital overlaps confirmed the presence of different chemical bonding in the Zn–P networks in the Cl- and Br-containing compounds. La3Zn4P6Cl was predicted to be a narrow bandgap semiconductor, while the formation of the [P3]3– units in the structure of La3Zn4P6.6Br0.8 was shown to lead to a narrowing of the bandgap. Characterization of the transport properties confirmed both La3Zn4P6Cl and La3Zn4P6.6Br0.8 to be narrow bandgap semiconductors with electrons as dominating charge carriers at low temperatures. La3Zn4P6Cl exhibits a n-p transition around 250 K. Due to the complex crystal structure and segregation of the areas of different chemical bonding, both title compounds exhibit ultralow thermal conductivities of 0.7 Wm–1 K–1 and 1.5 Wm–1 K–1 at 400 K for La3Zn4P6Cl and La3Zn4P6.6Br0.8, respectively.

    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.chemmater.6b01752.

    • Powder X-ray diffraction, EDX, details pertaining to the calculations, NMR results, and additional thermoelectric properties of La3Zn4P6Cl (PDF)

    • Crystallographic data for La3Zn4P6Cl (CIF)

    • Crystallographic data for La3Zn4P6.6Br0.8 (CIF)

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    Chemistry of Materials

    Cite this: Chem. Mater. 2016, 28, 13, 4741–4750
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.6b01752
    Published June 7, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

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