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Title: An Aluminum-Based Metal–Organic Cage for Cesium Capture

Abstract

Metal–organic cages are a class of supramolecular structures that often require the careful selection of organic linkers and metal nodes. Of this class, few examples of metal–organic cages exist where the nodes are composed of main group metals. Herein, we have prepared an aluminum-based metal–organic cage, H8[Al8(pdc)8(OAc)8O4] (Al-pdc-AA), using inexpensive and commercially available materials. The cage formation was achieved via solvothermal self-assembly of solvated aluminum and pyridine-dicarboxylic linkers in the presence of a capping agent, acetic acid. The obtained supramolecular structure was characterized by single-crystal X-ray diffraction (SCXRD), thermogravimetric analysis, and NMR spectroscopy. Based on crystal structure and computational analyses, the cage has a 3.7 Å diameter electron-rich cavity suitable for the binding of cations such as cesium (ionic radius of 1.69 Å). Here, the host–guest interactions were probed with 1H and 133Cs NMR spectroscopy in DMSO, where at low concentrations, Cs+ binds to Al-pdc-AA in a 1:1 ratio. The binding site was identified from the crystal structure of CsH7[Al8(pdc)8(OAc)8O4] (Cs+Al-pdc-AA), and a binding affinity of ~106–107 M–1 was determined from NMR titration experiments. The Al-pdc-AA showed improved selectivity for cesium binding over alkali metal cations (Cs+ > Rb+ > K+ >> Na+ ~ Li+). Collectively, the study reports amore » novel aluminum cage that can serve as a promising host for efficient and selective cesium removal.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Publication Date:
Research Org.:
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1890494
Grant/Contract Number:  
SC0012445
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 61; Journal Issue: 17; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Aluminum; Cations; Crystal structure; Nuclear magnetic resonance spectroscopy; Solvents

Citation Formats

Ilic, Stefan, May, Ann M., Usov, Pavel M., Cornell, Hannah D., Gibbons, Bradley, Celis-Salazar, Paula, Cairnie, Daniel R., Alatis, James, Slebodnick, Carla, and Morris, Amanda J. An Aluminum-Based Metal–Organic Cage for Cesium Capture. United States: N. p., 2022. Web. doi:10.1021/acs.inorgchem.2c00445.
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Ilic, Stefan, May, Ann M., Usov, Pavel M., Cornell, Hannah D., Gibbons, Bradley, Celis-Salazar, Paula, Cairnie, Daniel R., Alatis, James, Slebodnick, Carla, & Morris, Amanda J. An Aluminum-Based Metal–Organic Cage for Cesium Capture. United States. https://doi.org/10.1021/acs.inorgchem.2c00445
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Ilic, Stefan, May, Ann M., Usov, Pavel M., Cornell, Hannah D., Gibbons, Bradley, Celis-Salazar, Paula, Cairnie, Daniel R., Alatis, James, Slebodnick, Carla, and Morris, Amanda J. Thu . "An Aluminum-Based Metal–Organic Cage for Cesium Capture". United States. https://doi.org/10.1021/acs.inorgchem.2c00445. https://www.osti.gov/servlets/purl/1890494.
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@article{osti_1890494,
title = {An Aluminum-Based Metal–Organic Cage for Cesium Capture},
author = {Ilic, Stefan and May, Ann M. and Usov, Pavel M. and Cornell, Hannah D. and Gibbons, Bradley and Celis-Salazar, Paula and Cairnie, Daniel R. and Alatis, James and Slebodnick, Carla and Morris, Amanda J.},
abstractNote = {Metal–organic cages are a class of supramolecular structures that often require the careful selection of organic linkers and metal nodes. Of this class, few examples of metal–organic cages exist where the nodes are composed of main group metals. Herein, we have prepared an aluminum-based metal–organic cage, H8[Al8(pdc)8(OAc)8O4] (Al-pdc-AA), using inexpensive and commercially available materials. The cage formation was achieved via solvothermal self-assembly of solvated aluminum and pyridine-dicarboxylic linkers in the presence of a capping agent, acetic acid. The obtained supramolecular structure was characterized by single-crystal X-ray diffraction (SCXRD), thermogravimetric analysis, and NMR spectroscopy. Based on crystal structure and computational analyses, the cage has a 3.7 Å diameter electron-rich cavity suitable for the binding of cations such as cesium (ionic radius of 1.69 Å). Here, the host–guest interactions were probed with 1H and 133Cs NMR spectroscopy in DMSO, where at low concentrations, Cs+ binds to Al-pdc-AA in a 1:1 ratio. The binding site was identified from the crystal structure of CsH7[Al8(pdc)8(OAc)8O4] (Cs+Al-pdc-AA), and a binding affinity of ~106–107 M–1 was determined from NMR titration experiments. The Al-pdc-AA showed improved selectivity for cesium binding over alkali metal cations (Cs+ > Rb+ > K+ >> Na+ ~ Li+). Collectively, the study reports a novel aluminum cage that can serve as a promising host for efficient and selective cesium removal.},
doi = {10.1021/acs.inorgchem.2c00445},
journal = {Inorganic Chemistry},
number = 17,
volume = 61,
place = {United States},
year = {Thu Apr 21 00:00:00 EDT 2022},
month = {Thu Apr 21 00:00:00 EDT 2022}
}
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https://doi.org/10.1021/acs.inorgchem.2c00445
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