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Alternative to the Popular Imidazolium Ionic Liquids: 1,2,4-Triazolium Ionic Liquids with Enhanced Thermal and Chemical Stability

  • Deepak Chand
    Deepak Chand
    Department of Materials Science and Engineering, Iowa State University, 528 Bissell Road, Ames, Iowa 50012, United States
    Ames Laboratory, US Department of Energy and Critical Materials Institute, 2332 Pammel Drive, Ames, Iowa 50011, United States
    More by Deepak Chand
  • Magdalena Wilk-Kozubek
    Magdalena Wilk-Kozubek
    Department of Materials Science and Engineering, Iowa State University, 528 Bissell Road, Ames, Iowa 50012, United States
    Ames Laboratory, US Department of Energy and Critical Materials Institute, 2332 Pammel Drive, Ames, Iowa 50011, United States
    Department of Materials and Environmental Chemistry, Stockholm University, Svante Arrhenius väg 16 C, Stockholm 10691, Sweden
    ŁUKASIEWICZ Research Network - PORT Polish Center for Technology Development, 147 Stabłowicka Street, 54-066 Wrocław, Poland
  • Volodymyr Smetana
    Volodymyr Smetana
    Ames Laboratory, US Department of Energy and Critical Materials Institute, 2332 Pammel Drive, Ames, Iowa 50011, United States
    Department of Materials and Environmental Chemistry, Stockholm University, Svante Arrhenius väg 16 C, Stockholm 10691, Sweden
  • , and 
  • Anja-Verena Mudring*
    Anja-Verena Mudring
    Department of Materials Science and Engineering, Iowa State University, 528 Bissell Road, Ames, Iowa 50012, United States
    Ames Laboratory, US Department of Energy and Critical Materials Institute, 2332 Pammel Drive, Ames, Iowa 50011, United States
    Department of Materials and Environmental Chemistry, Stockholm University, Svante Arrhenius väg 16 C, Stockholm 10691, Sweden
    *E-mail: [email protected]
Cite this: ACS Sustainable Chem. Eng. 2019, 7, 19, 15995–16006
Publication Date (Web):August 16, 2019
https://doi.org/10.1021/acssuschemeng.9b02437
Copyright © 2019 American Chemical Society
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Supporting Info (1)»

Abstract

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Direct quaternization of 1-methyl-1,2,4-triazole with n-alkyl methanesulfonates (alkyl = butyl, octyl, dodecyl) showed to be an atom-economic, convenient, mild, solvent- and halide-free way to obtain 1,2,4-triazolium methanesulfonate ionic liquids in high purity and yield. Subsequent metathesis with lithium bis(trifluoromethanesulfonyl)amide (LiTf2N) allows for a much desired, easy access to halide-free, bis(trifluoromethanesulfonyl)amide ionic liquids. Differential scanning calorimetry confirms that all investigated compounds qualify as ionic liquids (ILs). Moreover, it reveals for 1-methyl-4-n-dodecyl-1,2,4-triazolium methanesulfonate a rather complex thermal behavior involving formation of mesophases. Indeed, polarizing optical microscopy shows oily streaky textures that are characteristic for smectic liquid crystalline phases. Single-crystal X-ray diffraction structure analysis confirms formation of a layered structure. All compounds are photoluminescent. The color of fluorescence at room temperature can be tuned from blue to orange through the length of the alkyl side chain of the cation, the aromatic interactions between the cations, and the anion nature. In addition, at low temperatures (77 K) a close to white phosphorescence with average lifetimes in the millisecond time range can be observed for 1-methyl-4-n-butyl-triazolium methanesulfonate and all of the studied bis(trifluoromethanesulfonyl)amide ILs. All ILs show an appreciable liquidus range and thermal (up to 260–350 °C) and electrochemical stability. The presented set of ILs overcomes the sometimes problematic acidity and low stability of imidazolium ILs in basic environment and can be obtained easily in high purity without halide contamination. Overcoming two shortcomings of classical imidazolium ILs, they may be good alternatives for a number of applications and even enabling new ones.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.9b02437.

  • 1H and 13C NMR spectra, FTIR spectra, evolved gas analysis, CV curves, fluorescence and phosphorescence decay curves (PDF)

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CCDC 1568074 and 1568073 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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This article is cited by 18 publications.

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