Nuclear magnetic resonance study on rotational dynamics of water and benzene in a series of ionic liquids: Anion and cation effects.

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The rotational correlation times (τ(2R)) for polar water (D(2)O) molecule and apolar benzene (C(6)D(6)) molecule were determined in ionic liquids (ILs) by means of the (2)H (D) NMR spin-lattice relaxation time (T(1)) measurements. The solvent IL was systematically varied to elucidate the anion and cation effects separately. Five species, bis(trifluoromethylsulfonyl)imide (TFSI(-)), trifluoromethylsulfonate (TfO(-)), hexafluorophosphate (PF(6) (-)), chloride (Cl(-)), and formate (HCOO(-)), were examined for the anion effect against a fixed cation species of 1-butyl-3-methyl-imidazolium (bmim(+)). Four species, bmim(+), N-methyl-N-butylpyrrolidinium (bmpy(+)), N,N,N-trimethyl-N-propylammonium (N(1,1,1,3) (+)), and P,P,P-trihexyl-P-tetradecylphosphonium (P(6,6,6,14) (+)), were employed for the cation effect against a fixed anion species of TFSI(-). The τ(2R) ratio of water to benzene, expressed as τ(W∕B), was used as a probe to characterize the strength of Coulombic solute-solvent interaction in ILs beyond the hydrodynamic limit based on the excluded-volume effect. The τ(W∕B) value was found to strongly depend on the anion species, and the solute dynamics are sensitive not only to the size but also to the chemical structure of the component anion. The cation effect was rather weak, in contrast. The largest and most hydrophobic P(6,6,6,14) (+) cation was exceptional and a large τ(W∕B) was observed, indicating a unique solvation structure in [P(6,6,6,14) (+)]-based ILs.


  • The Journal of chemical physics

    The Journal of chemical physics 137(19), 2012-11-21

    American Institute of Physics


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