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Thermal and Electro...
Thermal and Electrochemical Stability of Tetraglyme-Magnesium Bis(trifluoromethanesulfonyl)amide Complex: Electric Field Effect of Divalent Cation on Solvate Stability
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- Terada, S. (author)
- Yokohama National University
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- Mandai, Toshihiko, 1984 (author)
- Yokohama National University
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- Suzuki, S. (author)
- Yokohama National University
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- Tsuzuki, S. (author)
- National Institute of Advanced Industrial Science and Technology (AIST)
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- Watanabe, K. (author)
- Yokohama National University
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- Kamei, Y. (author)
- Yokohama National University
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- Ueno, K. (author)
- Yokohama National University
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- Dokko, K. (author)
- Yokohama National University,Kyoto University
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- Watanabe, M. (author)
- Yokohama National University
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(creator_code:org_t)
- 2016-01-13
- 2016
- English.
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In: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 120:3, s. 1353-1365
- Related links:
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http://dx.doi.org/10...
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https://doi.org/10.1...
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Abstract
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- Phase behavior of binary mixtures of tetraglyme (G4) and Mg[TFSA]2 (TFSA: bis(trifluoromethanesulfonyl)amide) was investigated. In a 1:1 molar ratio, G4 and Mg[TFSA]2 formed a stable complex with a melting point of 137 degrees C. X-ray crystallography of a single crystal of the complex grown from a G4-Mg[TFSA]2 binary mixture revealed that the G4 molecule wraps around Mg2+ to form a complex [Mg(G4)](2+) cation, and the two [TFSA](-) anions also participate in the Mg2+ coordination in the crystal. The thermal stability of [Mg(G4)][TFSA](2) was examined by thermogravimetry, and it was found that the complex is stable up to 250 degrees C. Above 250 degrees C, desolvation of the Mg2+ ion takes place and G4 evaporates. On the other hand, the weight loss starts at around 140 degrees C in solutions containing excess G4 (n > 1 in Mg[TFSA]2:G4 = 1:n) due to the evaporation of free (uncoordinated) G4. The suppression of G4 volatility in the [Mg(G4)][TFSA]2 complex is attributed to strong electrostatic and induction interactions between divalent Mg2+ and G4. In addition, complexation of G4 with Mg2+ is effective in enhancing the oxidative stability of G4. Linear sweep voltammetry revealed that the oxidative decomposition of [Mg(G4)][TFSA]2 occurs at electrode potentials >5 V vs Li/Li+, while the oxidation of uncoordinated G4 occurs at around 4.0 V. This oxidative stability enhancement occurs because the HOMO energy level of G4 is reduced by complexation with Mg2+, which is supported by the ab initio calculations.
Subject headings
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
Keyword
Publication and Content Type
- art (subject category)
- ref (subject category)
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