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Neutron Diffraction Study of Significant sp3 and sp2 C–H Bond Shortening in a Fluorinated Pyridinium Saccharinate
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    Neutron Diffraction Study of Significant sp3 and sp2 C–H Bond Shortening in a Fluorinated Pyridinium Saccharinate
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    • Norman Lu*
      Norman Lu
      Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
      Development Center for Smart Textile, National Taipei University of Technology, Taipei 106, Taiwan, ROC
      *[email protected]
      More by Norman Lu
    • Vijayanath Elakkat
      Vijayanath Elakkat
      Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
    • Joseph S. Thrasher*
      Joseph S. Thrasher
      Department of Chemistry, Advanced Materials Research Laboratory, Clemson University, Anderson, South Carolina 29625, United States
      *[email protected]
    • Xiaoping Wang*
      Xiaoping Wang
      Neutron Scattering Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      *[email protected]
    • Eskedar Tessema
      Eskedar Tessema
      Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
    • Ka Long Chan
      Ka Long Chan
      Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
      More by Ka Long Chan
    • Rong-Jun Wei
      Rong-Jun Wei
      Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
      More by Rong-Jun Wei
    • Tarek Trabelsi
      Tarek Trabelsi
      Department of Earth and Environmental Science and Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6316, United States
    • Joseph S. Francisco*
      Joseph S. Francisco
      Department of Earth and Environmental Science and Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6316, United States
      *[email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 14, 5550–5557
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.1c02570
    Published March 30, 2021
    Copyright © 2021 American Chemical Society

    Abstract

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    We have experimentally shown by neutron diffraction significant shortening of both sp3- and sp2-hybridized C–H bonds to 1.092(2) and 1.081(1) Å in a hydrogen-bonded crystal of a difluorinated compound, 4-((2,2-difluoroethoxy)methyl)pyridinium saccharinate. Both MP2 and DFT calculations affirmed the C–H bond shrinkages. Sanderson’s electronegativity equalization principle provides insight into the shortening of the C–H covalent bond lengths for both sp3- and sp2-hybridized carbon atoms. To the best of our knowledge, this neutron diffraction study has revealed the largest extents of sp3 and sp2 C–H bond shrinkages with a 3-sigma rule being satisfied.

    Copyright © 2021 American Chemical Society

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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/jacs.1c02570.

    • Synthesis, characterization data, and single-crystal X-ray/neutron methods, including Figures S1–S5, Tables S1–S13, and Schemes S1 and S2 (PDF)

    Accession Codes

    CCDC 1953916, 2003417, and 2013378 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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    Cited By

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    This article is cited by 15 publications.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 14, 5550–5557
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.1c02570
    Published March 30, 2021
    Copyright © 2021 American Chemical Society

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