ACS Publications. Most Trusted. Most Cited. Most Read
Leveraging Nitrogen Linkages in the Formation of a Porous Thorium–Organic Nanotube Suitable for Iodine Capture

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2022, 61, 25, 9480-9492
    Article

    Leveraging Nitrogen Linkages in the Formation of a Porous Thorium–Organic Nanotube Suitable for Iodine Capture
    Click to copy article linkArticle link copied!

    • 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
      More by Ashley M. Hastings
    • 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
      Orcidhttps://orcid.org/0000-0002-8309-8183
    • Sylvia L. Hanna
      Sylvia L. Hanna
      Department of Chemistry, International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
      More by Sylvia L. Hanna
    • 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
      More by WooSeok Jeong
    • 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
      Orcidhttps://orcid.org/0000-0001-9232-7382
    • Allen G. Oliver
      Allen G. Oliver
      Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States
      More by Allen G. Oliver
      Orcidhttps://orcid.org/0000-0002-0511-1127
    • 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
      More by Laura Gagliardi
      Orcidhttps://orcid.org/0000-0001-5227-1396
    • Omar K. Farha
      Omar K. Farha
      Department of Chemistry, International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
      More by Omar K. Farha
    • 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
    Other Access OptionsSupporting Information (2)

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2022, 61, 25, 9480–9492
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.2c00427
    Published June 14, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    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.

    Copyright © 2022 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    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)

    Accession Codes

    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.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 13 publications.

    1. Kyoung Chul Park, Jaewoong Lim, Grace C. Thaggard, Natalia B. Shustova. Mining for Metal–Organic Systems: Chemistry Frontiers of Th-, U-, and Zr-Materials. Journal of the American Chemical Society 2024, 146 (27) , 18189-18204. https://doi.org/10.1021/jacs.4c06088
    2. Jaewoong Lim, Kyoung Chul Park, Grace C. Thaggard, Yuan Liu, Buddhima K. P. Maldeni Kankanamalage, Donald J. Toler, An T. Ta, Preecha Kittikhunnatham, Mark D. Smith, Simon R. Phillpot, Natalia B. Shustova. Friends or Foes: Fundamental Principles of Th-Organic Scaffold Chemistry Using Zr-Analogs as a Guide. Journal of the American Chemical Society 2024, 146 (17) , 12155-12166. https://doi.org/10.1021/jacs.4c02327
    3. Noorullah Baig, Suchetha Shetty, Sk Abdul Wahed, Atikur Hassan, Neeladri Das, Bassam Alameddine. Promising CO2 Capture and Effective Iodine Adsorption of Hyper-Cross-Linked Conjugated Porous Organic Polymers Prepared from a Cyclopentannulation Reaction. ACS Applied Materials & Interfaces 2024, Article ASAP.
    4. Susan Sen, Rasha Diab, Mohammad H. Al-Sayah, Ribal Jabbour, Asif Equbal, Oussama M. El-Kadri. Selective Carbon Dioxide Capture and Ultrahigh Iodine Uptake by Tetraphenylethylene-Functionalized Nitrogen-Rich Porous Organic Polymers. ACS Applied Polymer Materials 2024, 6 (2) , 1314-1324. https://doi.org/10.1021/acsapm.3c02341
    5. Noorullah Baig, Suchetha Shetty, Rupa Bargakshatriya, Sumit Kumar Pramanik, Bassam Alameddine. Efficient Iodine Uptake of Ultra Thermally Stable Conjugated Copolymers Bearing Biaceanthrylenyl Moieties and Contorted Aromatic Units Using a [3 + 2] Palladium-Catalyzed Cyclopolymerization Reaction. ACS Omega 2023, 8 (45) , 43227-43235. https://doi.org/10.1021/acsomega.3c07108
    6. Turki Alghamdi, Peter O. Aina, Ali A. Rownaghi, Fateme Rezaei. Influence of Interfering Ions and Adsorption Temperature on Radioactive Iodine Removal Efficiency and Stability of Ni-MOF-74 and Zr-UiO-66. ACS Applied Materials & Interfaces 2023, 15 (28) , 33621-33632. https://doi.org/10.1021/acsami.3c05821
    7. Yu Ju, Zi-Jian Li, Jie Qiu, Xiaoyun Li, Junpu Yang, Zhi-Hui Zhang, Ming-Yang He, Jian-Qiang Wang, Jian Lin. Adsorption and Detection of Iodine Species by a Thorium-Based Metal–Organic Framework. Inorganic Chemistry 2023, 62 (21) , 8158-8165. https://doi.org/10.1021/acs.inorgchem.3c00473
    8. Kai Lv, Michael Patzschke, Juliane März, Elena Bazarkina, Kristina O. Kvashnina, Moritz Schmidt. Selective Crystallization of a Highly Radiation-Resistant Isonicotinic Acid-Based Metal–Organic Framework as a Primary Actinide Waste Form. ACS Materials Letters 2023, 5 (2) , 536-542. https://doi.org/10.1021/acsmaterialslett.2c01087
    9. Zhi-Hao Zhang, Jia-Lu Ge, Yan Li, Qing Li, Pin-Pin Ma, Xiao-Yan Tang, Wen-Hua Zhang, David J. Young. Two-dimensional Cd 3 -based metal–organic frameworks with halogen bonding sites for the uptake of I 2. CrystEngComm 2023, 25 (12) , 1775-1781. https://doi.org/10.1039/D2CE01582J
    10. Zhaofa Zheng, Huangjie Lu, Huiliang Hou, Yaoyao Bai, Jie Qiu, Xiaofeng Guo, Jian‐Qiang Wang, Jian Lin. Stepwise Crystallization of Millimeter Scale Thorium Cluster Single Crystals as a Bifunctional Platform for X‐ray Detection and Shielding. Small 2023, 19 (10) , 2206782. https://doi.org/10.1002/smll.202206782
    11. Yiran Fu, Xue Wang, Yu Ju, Zhaofa Zheng, Jie Jian, Zi-Jian Li, Chan Jin, Jian-Qiang Wang, Jian Lin. A robust thorium–organic framework as a bifunctional platform for iodine adsorption and Cr( vi ) sensitization. Dalton Transactions 2023, 52 (5) , 1177-1181. https://doi.org/10.1039/D2DT03623A
    12. Suchetha Shetty, Noorullah Baig, Bassam Alameddine. Synthesis and Iodine Adsorption Properties of Organometallic Copolymers with Propeller-Shaped Fe(II) Clathrochelates Bridged by Different Diaryl Thioether and Their Oxidized Sulfone Derivatives. Polymers 2022, 14 (22) , 4818. https://doi.org/10.3390/polym14224818
    13. Noorullah Baig, Suchetha Shetty, Sameh S. Habib, Ali A. Husain, Saleh Al-Mousawi, Bassam Alameddine. Synthesis of Iron(II) Clathrochelate-Based Poly(vinylene sulfide) with Tetraphenylbenzene Bridging Units and Their Selective Oxidation into Their Corresponding Poly(vinylene sulfone) Copolymers: Promising Materials for Iodine Capture. Polymers 2022, 14 (18) , 3727. https://doi.org/10.3390/polym14183727
    Download PDF
    Go to Inorganic Chemistry
    Get e-Alerts
    Get e-Alerts

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2022, 61, 25, 9480–9492
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.2c00427
    Published June 14, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

    Article Views

    1399

    Altmetric

    -

    Citations

    13
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.