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Changes in the Electronic Transitions of Polyethylene Glycol upon the Formation of a Coordinate Bond with Li+, Studied by ATR Far-Ultraviolet Spectroscopy

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    Changes in the Electronic Transitions of Polyethylene Glycol upon the Formation of a Coordinate Bond with Li+, Studied by ATR Far-Ultraviolet Spectroscopy
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    • Nami Ueno
      Nami Ueno
      Department of Science, Graduate School of Science and Engineering, Kindai University, 3-4-1 Kowakae, Higashi-Osaka City 577-8502, Japan
      More by Nami Ueno
    • Tomonari Wakabayashi
      Tomonari Wakabayashi
      Department of Science, Graduate School of Science and Engineering  and  Department of Science, Faculty of Science and Engineering, Kindai University, 3-4-1 Kowakae, Higashi-Osaka City 577-8502, Japan
      More by Tomonari Wakabayashi
    • Harumi Sato
      Harumi Sato
      Graduate School of Human Development and Environment, Kobe University, 3-11 Tsurukabuto Nada-ku, Kobe 657-8501, Japan
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    • Yusuke Morisawa*
      Yusuke Morisawa
      Department of Science, Graduate School of Science and Engineering  and  Department of Science, Faculty of Science and Engineering, Kindai University, 3-4-1 Kowakae, Higashi-Osaka City 577-8502, Japan
      *E-mail: [email protected]
      More by Yusuke Morisawa
      Orcidhttp://orcid.org/0000-0001-7109-7047
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2019, 123, 50, 10746–10756
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.9b09274
    Published November 15, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    This study investigates the electronic transitions of complexes of lithium with polyethylene glycol (PEG) by the absorption bands of solvent molecules via attenuated total reflectance spectroscopy in the far-UV region (ATR–FUV). Alkali-metal complexes are interesting materials because of their functional characteristics such as good ionic conductivity. These complexes are used as polymer electrolytes for Li batteries and as one of the new types of room-temperature ionic liquids, termed solvation ionic liquids. Considering these applications, alkali-metal complexes have been studied mainly for their electrochemical characteristics; there is no fundamental study providing a clear understanding of electronic states in terms of electronic structures for the ground and excitation states near the highest occupied molecular orbital–lowest occupied molecular orbital transitions. This study explores the electronic transitions of ligand molecules in alkali-metal complexes. In the ATR–FUV spectra of the Li–PEG complex, a decrease in intensity and a large blue shift (over 4 nm) were observed to result from an increase in the concentration of Li salts. This observation suggests the formation of a complex, with coordinate bonding between Li+ and the O atoms in PEG. Comparison of the experimental spectrum with a simulated spectrum of the Li–PEG complex calculated by time-dependent density functional theory indicated that changes in the intensities and peak positions of bands at approximately 155 and 177 nm (pure PEG shows bands at 155, 163, and 177 nm) are due to the formation of coordinate bonding between Li+ and the O atoms in the ether molecule. The intensity of the 177 nm band depends on the number of residual free O atoms in the ether, and the peak wavelength at approximately 177 nm changes with the expansion of the electron clouds of PEG. We assign a band in the 145–155 nm region to the alkali-metal complex because we observed a new band at approximately 150 nm in the ATR–FUV spectra of very highly concentrated binary mixtures.

    Copyright © 2019 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/acs.jpca.9b09274.

    • Chemical structures of the solvent and solute molecules, ATR–FUV spectra of Li salts in powder state, second-derivative spectra of the complexes included with Li salt and TEGDM, dependence of the peak wavelength on the average molecular weight of PEG, and molecular orbitals near HOMO–LUMO orbitals about Int 1 (high C model) and Int 3 (PDF)

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    Cited By

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    This article is cited by 16 publications.

    1. Bethany F. Laatsch, Michael Brandt, Brianna Finke, Carl J. Fossum, Miles J. Wackett, Harrison R. Lowater, Alex Narkiewicz-Jodko, Christine N. Le, Thao Yang, Elizabeth M. Glogowski, Scott C. Bailey-Hartsel, Sudeep Bhattacharyya, Sanchita Hati. Polyethylene Glycol 20k. Does It Fluoresce?. ACS Omega 2023, 8 (15) , 14208-14218. https://doi.org/10.1021/acsomega.3c01124
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    13. Yusuke Morisawa, Erika Tanimura, Masahiro Ehara, Harumi Sato. Attenuated Total Reflection–Far-Ultraviolet Spectroscopy and Quantum Chemical Calculations of the Electronic Structure of the Top Surface and Bulk of Polyethylenes with Different Crystallinities. Applied Spectroscopy 2021, 75 (8) , 971-979. https://doi.org/10.1177/00037028211013425
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    15. Masaya Imai, Ichiro Tanabe, Akifumi Ikehata, Yukihiro Ozaki, Ken-ichi Fukui. Attenuated total reflectance far-ultraviolet and deep-ultraviolet spectroscopy analysis of the electronic structure of a dicyanamide-based ionic liquid with Li +. Physical Chemistry Chemical Physics 2020, 22 (38) , 21768-21775. https://doi.org/10.1039/D0CP03865B
    16. Nami Ueno, Tomonari Wakabayashi, Yusuke Morisawa. Determining the Coordination Number of Li+ and Glyme or Poly(ethylene glycol) in Solution Using Attenuated Total Reflectance-Far Ultraviolet Spectroscopy. Analytical Sciences 2020, 36 (1) , 91-93. https://doi.org/10.2116/analsci.19C011
    17. Yukihiro Ozaki. Advances in Molecular Spectroscopy in Condensed Phase and Quantum Chemistry. Molecular Science 2020, 14 (1) , A0114. https://doi.org/10.3175/molsci.14.A0114
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2019, 123, 50, 10746–10756
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.9b09274
    Published November 15, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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