ACS Publications. Most Trusted. Most Cited. Most Read
Neutron Diffraction Study of Significant sp3 and sp2 C–H Bond Shortening in a Fluorinated Pyridinium Saccharinate

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Am. Chem. Soc. 2021, 143, 14, 5550-5557
    Article

    Neutron Diffraction Study of Significant sp3 and sp2 C–H Bond Shortening in a Fluorinated Pyridinium Saccharinate
    Click to copy article linkArticle link copied!

    • 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
      Orcidhttp://orcid.org/0000-0002-3554-6113
    • Vijayanath Elakkat
      Vijayanath Elakkat
      Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
      More by Vijayanath Elakkat
    • Joseph S. Thrasher*
      Joseph S. Thrasher
      Department of Chemistry, Advanced Materials Research Laboratory, Clemson University, Anderson, South Carolina 29625, United States
      *[email protected]
      More by Joseph S. Thrasher
      Orcidhttp://orcid.org/0000-0003-1479-1897
    • Xiaoping Wang*
      Xiaoping Wang
      Neutron Scattering Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      *[email protected]
      More by Xiaoping Wang
      Orcidhttp://orcid.org/0000-0001-7143-8112
    • Eskedar Tessema
      Eskedar Tessema
      Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
      More by Eskedar Tessema
    • 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
      More by Tarek Trabelsi
      Orcidhttp://orcid.org/0000-0001-6258-7191
    • 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]
      More by Joseph S. Francisco
      Orcidhttp://orcid.org/0000-0002-5461-1486
    Other Access OptionsSupporting Information (1)

    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
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    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

    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/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.

    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 15 publications.

    1. Gurumallappa Gurumallappa, Chiao-Fan Chiu, Chi-Liang Ho, Huan-Cheng Chang, Hema Mylnahalli Krishnegowda, Neratur Krishnappagowda Lokanath, Peng Zhang, Norman Lu. Synthesis, structure and non-covalent interactions of trans-[2-(HCF2(CF2)3CH2OCH2)2-py-PdCl2] complex: Rare C−F⋯F−C halogen bonds and blue-shifting C−H⋯X hydrogen bonds. Journal of Molecular Structure 2025, 1322 , 140303. https://doi.org/10.1016/j.molstruc.2024.140303
    2. Guanjie Huang, Jianzhong Ma, Jie Chen, Wenbo Zhang, Qianqian Fan, Buxing Han. Controllable Strategy of Metal–Organic Framework Structural Stability: Regulation of Ligand Electronegativity by Esterification. Advanced Science 2024, 146 https://doi.org/10.1002/advs.202413853
    3. Md. Sajid Hasan, Muhammad Abul Kashem Liton, Shathee Akter. Synthesis, spectroscopic characterisation, DFT insight, and molecular docking studies of a coumarin derivative 3-acetyl-2-oxo-2H-chromene-6-carbohydrazide. Molecular Physics 2024, 122 (14) https://doi.org/10.1080/00268976.2024.2307491
    4. C.S. Karthik, N. Maithra, A.H. Udaya Kumar, Jothi Ramalingam Rajabathar, K.P. Sukrutha, M.K. Hema, N.K. Lokanath. Exploration of one-dimensional hydrogen bonding organic framework (1D-HOF) and charge transfer dynamics in N’-benzylbenzohydrazide: A comprehensive structural and quantum computational investigation. Journal of Molecular Structure 2024, 1307 , 137845. https://doi.org/10.1016/j.molstruc.2024.137845
    5. Michal Szczygiel, Urszula Derewenda, Steve Scheiner, Wladek Minor, Zygmunt S. Derewenda. A structural role for tryptophan in proteins, and the ubiquitous Trp C δ1 —H...O=C (backbone) hydrogen bond. Acta Crystallographica Section D Structural Biology 2024, 80 (7) , 551-562. https://doi.org/10.1107/S2059798324005515
    6. B.L. Vinay, C.S. Karthik, M.K. Hema, Jothi Ramalingam Rajabathar, A.H. Udaya Kumar, B.N. Ramakrishna, N.K. Lokanath. Non-covalent interactions orchestrated distinct molecular arrangements along different axes within the novel mixed ligand thorium metal complex: Experimental and theoretical insights. Journal of Molecular Structure 2024, 1303 , 137486. https://doi.org/10.1016/j.molstruc.2024.137486
    7. M.K. Hema, C.S. Karthik, Jothi Ramalingam Rajabathar, Hamad A. Al Lohedan, Hassan Alsaigh, Selvaraj Arokiyaraj, Dafellah M Aldayan, N.K. Lokanath. A new mixed-ligand mononuclear Co(II) complex derived from 4,4,4-trifluoro-1-phenylbutane-1,3-dione and 1,10-phenanthroline: Synthesis, structural elucidation and quantum-computational studies. Journal of Molecular Structure 2024, 1299 , 137169. https://doi.org/10.1016/j.molstruc.2023.137169
    8. T.N. Lohith, M.K. Hema, C.S. Karthik, Sandeep S, Jothi Ramalingam Rajabathar, Muthusamy Karnan, N.K. Lokanath, L. Mallesha, P. Mallu, M.A. Sridhar. Probing the hydrogen bond network in the crystal structure of a sulfonamide derivative: A quantum chemical approach. Journal of Molecular Structure 2023, 1289 , 135841. https://doi.org/10.1016/j.molstruc.2023.135841
    9. Vijayanath Elakkat, Eskedar Tessema, Chia‐Her Lin, Xiaoping Wang, Huan‐Cheng Chang, You‐Ning Zheng, Yu‐Cheng Huang, Gurumallappa, Zhong‐Yun Zhang, Ka Long Chan, Hening A. Rahayu, Joseph S. Francisco, Norman Lu. Unusual Changes of C−H Bond Lengths in Chiral Zinc Complexes Induced by Noncovalent Interactions. Angewandte Chemie 2023, 135 (6) https://doi.org/10.1002/ange.202215438
    10. Vijayanath Elakkat, Eskedar Tessema, Chia‐Her Lin, Xiaoping Wang, Huan‐Cheng Chang, You‐Ning Zheng, Yu‐Cheng Huang, Gurumallappa, Zhong‐Yun Zhang, Ka Long Chan, Hening A. Rahayu, Joseph S. Francisco, Norman Lu. Unusual Changes of C−H Bond Lengths in Chiral Zinc Complexes Induced by Noncovalent Interactions. Angewandte Chemie International Edition 2023, 62 (6) https://doi.org/10.1002/anie.202215438
    11. Gurumallappa, J. Jayashankar, M.K. Hema, C.S. Karthik, D. Suma, S.R. Kumaraswamy, N.K. Lokanath, P. Mallu, M. Nethaji, N. Lu. Enchant O H⋅⋅⋅O interactions in hydrated 6-amino-2-methoxypyrimidin-4(3H)one resembles as water flow in the channel: Crystallographic and theoretical investigations. Journal of Molecular Structure 2022, 1263 , 133098. https://doi.org/10.1016/j.molstruc.2022.133098
    12. Eskedar Tessema, Yao-Wen Fan, Chiao-Fan Chiu, Vijayanath Elakkat, Hening Asti Rahayu, Chia-Rui Shen, Karthik Chimatahalli Shanthakumar, Peng Zhang, Norman Lu. Recoverable low fluorine content palladium complex-catalyzed Suzuki-Miyaura and Sonogashira coupling reactions under thermomorphic mode. Tetrahedron 2022, 122 , 132961. https://doi.org/10.1016/j.tet.2022.132961
    13. Md. Sajid Hasan, Abul Kashem Liton, Tahmina Haque, Mohammad Idrish Ali, Shathee Akter. An experimental and DFT computational study on Methyl 3-acetyl-2-oxo-2H-chromene-6-carboxylate. Molecular Physics 2022, 120 (14) https://doi.org/10.1080/00268976.2022.2103468
    14. Guoping Li, Liang-Wen Feng, Subhrangsu Mukherjee, Leighton O. Jones, Robert M. Jacobberger, Wei Huang, Ryan M. Young, Robert M. Pankow, Weigang Zhu, Norman Lu, Kevin L. Kohlstedt, Vinod K. Sangwan, Michael R. Wasielewski, Mark C. Hersam, George C. Schatz, Dean M. DeLongchamp, Antonio Facchetti, Tobin J. Marks. Non-fullerene acceptors with direct and indirect hexa-fluorination afford >17% efficiency in polymer solar cells. Energy & Environmental Science 2022, 15 (2) , 645-659. https://doi.org/10.1039/D1EE03225A
    15. Eskedar Tessema, Yao-Wen Fan, Chiao-Fan Chiu, Vijayanath Elakkat, Hening Asti Rahayu, Chia-Rui Shen, Karthik Chimatahalli Shanthakumar, Norman Lu. Recoverable Low Fluorine Content Palladium Complex-Catalyzed Suzuki-Miyaura and Sonogashira Coupling Reactions Under Thermomorphic Mode. SSRN Electronic Journal 2022, 51 https://doi.org/10.2139/ssrn.4143735
    Download PDF
    Go to Journal of the American Chemical Society
    Get e-Alerts
    Get e-Alerts

    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
    Request reuse permissions

    Article Views

    5161

    Altmetric

    -

    Citations

    15
    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.