Fluorinated Boroxin-Based Anion Receptors for Lithium Ion Batteries: Fluoride Anion Binding, Ab Initio Calculations, and Ionic Conductivity Studies
Novel fluorinated boroxines, tris(2,6-difluorophenyl)boroxin (DF), tris(2,4,6-trifluorophenyl)boroxin (TF), and tris(pentafluorophenyl)boroxin (PF), have been investigated for potential applications in lithium ion batteries through fluoride anion binding, ab initio calculations, and ionic conductivity measurements. Structures of the fluorinated boroxines and boroxin-fluoride complexes have been confirmed by comparing their 19F and 11B NMR chemical shifts with those obtained by the DFT-GIAO method. The stoichiometry of the fluoride anion binding to these boroxines has been shown to be 1:1 using 19F NMR and UV-vis spectroscopy. UV-vis spectroscopic studies show the coexistence of more than one complex, in addition to the 1:1 complex, for perfluorinated boroxin, PF. DFT calculations (B3LYP/6-311G**) show that the fluoride ion complex of DF prefers unsymmetrical, covalently bound structure (7) over the symmetrically bridged species (10) by 12.5 kcal/mol. Rapid equilibration of the fluoride anion among the three borons in these boroxines results in a single 19F NMR absorption for all of the aromatic ortho-or para-fluorines at ambient temperature. The effect of these anion receptors on lithium ion conductivities was also explored for potential applications in dual ion intercalating lithium batteries.
N. G. Nair et al., "Fluorinated Boroxin-Based Anion Receptors for Lithium Ion Batteries: Fluoride Anion Binding, Ab Initio Calculations, and Ionic Conductivity Studies," The Journal of Physical Chemistry A, vol. 113, no. 20, pp. 5918-5926, American Chemical Society (ACS), May 2009.
The definitive version is available at http://dx.doi.org/10.1021/jp901952t
United States. Army Research Office
United States. National Aeronautics and Space Administration
Keywords and Phrases
Ab initio calculations; Ambient temperatures; Anion receptor; Boroxines; Conductivity measurements; Covalently bound; DFT calculation; Difluorophenyl; Fluoride anions; Fluoride complexes; Fluoride ion; Lithium-ion battery; Lithium-ion conductivity; NMR absorption; NMR chemical shifts; Pentafluorophenyl; Potential applications; Spectroscopic studies; Unsymmetrical; UV-vis spectroscopy; Boron; Fluorescence; Fluorine; Ionic conductivity; Lithium; Lithium alloys; Lithium compounds; Nuclear magnetic resonance; Nuclear magnetic resonance spectroscopy; Probability density function; Spectroscopic analysis; Stoichiometry; Sulfur compounds; Thermal effects; Ultraviolet spectroscopy; Negative ions
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