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Expansion of the Family of Molecular Nanoparticles of Cerium Dioxide and Their Catalytic Scavenging of Hydroxyl Radicals

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    Expansion of the Family of Molecular Nanoparticles of Cerium Dioxide and Their Catalytic Scavenging of Hydroxyl Radicals
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    • Kylie J. Mitchell
      Kylie J. Mitchell
      Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, United States
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    • Justin L. Goodsell
      Justin L. Goodsell
      Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, United States
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    • Bradley Russell-Webster
      Bradley Russell-Webster
      Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, United States
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    • Umar T. Twahir
      Umar T. Twahir
      Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, United States
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    • Alexander Angerhofer
      Alexander Angerhofer
      Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, United States
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      Orcidhttp://orcid.org/0000-0002-8580-6024
    • Khalil A. Abboud
      Khalil A. Abboud
      Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, United States
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    • George Christou*
      George Christou
      Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, United States
      *Email: [email protected]. Phone: +1-352-392-8314.
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      Orcidhttp://orcid.org/0000-0001-5923-5523
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2021, 60, 3, 1641–1653
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    https://doi.org/10.1021/acs.inorgchem.0c03133
    Published January 12, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    The syntheses, crystal structures, and catalytic radical scavenging activity are reported for four new molecular clusters that have resulted from a bottom-up molecular approach to nanoscale CeO2. They are [Ce6O4(OH)4(dmb)12(H2O)4] (dmb– = 2,6-dimethoxybenzoate), [Ce16O17(OH)6(O2CPh)24(HO2CPh)4], [Ce19O18(OH)9(O2CPh)27(H2O)(py)3], and [Ce24O27(OH)9(O2CPh)30(py)4]. They represent a major expansion of our family of so-called “molecular nanoparticles” of this metal oxide to seven members, and their crystal structures confirm that their cores all possess the fluorite structure of bulk CeO2. In addition, they have allowed the identification of surface features such as the close location of multiple Ce3+ ions and organic ligand binding modes not seen previously. The ability of all seven members to catalytically scavenge reactive oxygen species has been investigated using HO• radicals, an important test reaction in the ceria nanoparticle biomedical literature, and most have been found to exhibit excellent antioxidant activities compared to traditional ceria nanoparticles, with their activity correlating inversely with their surface Ce3+ content.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03133.

    • Ce and O BVS tables, structural figures, and EPR spectra for 6 and 7 (PDF)

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    CCDC 2024106–2024109 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2021, 60, 3, 1641–1653
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.0c03133
    Published January 12, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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