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Leveraging Nitrogen Linkages in the Formation of a Porous Thorium–Organic Nanotube Suitable for Iodine Capture

  • Ashley M. Hastings
    Ashley M. Hastings
    Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, 301 Stinson-Remick, Notre Dame, Indiana 46556, United States
  • Debmalya Ray
    Debmalya Ray
    Department of Chemistry, Chemical Theory Center and Minnesota Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455, United States
    More by Debmalya Ray
  • Sylvia L. Hanna
    Sylvia L. Hanna
    Department of Chemistry, International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
  • WooSeok Jeong
    WooSeok Jeong
    Department of Chemistry, Chemical Theory Center and Minnesota Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455, United States
  • Zhijie Chen
    Zhijie Chen
    Department of Chemistry, International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
    More by Zhijie Chen
  • Allen G. Oliver
    Allen G. Oliver
    Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States
  • Laura Gagliardi
    Laura Gagliardi
    Department of Chemistry, Pritzker School of Molecular Engineering, James Franck Institute, Chicago Center for Theoretical Chemistry, The University of Chicago, 5735 S. Ellis Ave., Chicago, Illinois 60637, United States
    Argonne National Laboratory, 97000 S. Cass Ave., Lemont, Illinois 60439, United States
  • Omar K. Farha
    Omar K. Farha
    Department of Chemistry, International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
  • , and 
  • Amy E. Hixon*
    Amy E. Hixon
    Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, 301 Stinson-Remick, Notre Dame, Indiana 46556, United States
    *Email: [email protected]
    More by Amy E. Hixon
Cite this: Inorg. Chem. 2022, 61, 25, 9480–9492
Publication Date (Web):June 14, 2022
https://doi.org/10.1021/acs.inorgchem.2c00427
Copyright © 2022 American Chemical Society

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    Abstract

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    We report the synthesis, characterization, and iodine capture application of a novel thorium–organic nanotube, TSN-626, [Th6O4(OH)4(C6H4NO2)7(CHO2)5(H2O)3]·3H2O. The classification as a metal–organic nanotube (MONT) distinguishes it as a rare and reduced dimensionality subset of metal–organic frameworks (MOFs); the structure is additionally hallmarked by low node connectivity. TSN-626 is composed of hexameric thorium secondary building units and mixed O/N-donor isonicotinate ligands that demonstrate selective ditopicity, yielding both terminating and bridging moieties. Because hard Lewis acid tetravalent metals have a propensity to bind with electron donors of rival hardness (e.g., carboxylate groups), such Th–N coordination in a MOF is uncommon. However, the formation of key structural Th–N bonds in TSN-626 cap some of the square antiprismatic metal centers, a position usually occupied by terminal water ligands. TSN-626 was characterized by using complementary analytical and computational techniques: X-ray diffraction, vibrational spectroscopy, N2 physisorption isotherms, and density functional theory. TSN-626 satisfies design aspects for the chemisorption of iodine. The synergy between accessibility through pores, vacancies at the metal–oxo nodes, and pendent N-donor sites allowed a saturated iodine loading of 955 mg g–1 by vapor methods. The crystallization of TSN-626 diversifies actinide–MOF linker selection to include soft electron donors, and these Th–N linkages can be leveraged for the investigation of metal-to-ligand bonding and unconventional topological expressions.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c00427.

    • More details on crystal structure and topology, characterization by SEM-EDS, PXRD, SAXS, N2 physisorption isotherms, pore size distribution simulations, FTIR, Raman, DOS, XPS, iodine uptake methodology, and TGA (PDF)

    • Optimized structures package for the periodic structure and truncated cluster models (ZIP)

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    CCDC 2097535 contains 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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    Cited By

    This article is cited by 12 publications.

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