State of anion in ethylammonium nitrate enclosed between micrometer-spaced glass plates as studied by 17O and 15N NMR

Abstract

Some aprotic and protic ionic liquids (ILs) containing nitrate anion demonstrate unusual dynamic behavior of cations when these ILs are enclosed in micrometer-spaced layers between glass plates. We applied ¹⁷O and ¹⁵N NMR spectroscopy to discover the state and transformations of ¹⁷O and ¹⁵N isotopically enriched nitrate anion of ethylammonium nitrate (EAN) enclosed between glass plates. ¹⁵N NMR spectra demonstrated preferential orientation of the principal axes of the nitrate anions perpendicular to the normal of the glass surface. Therefore, isotropic ionic liquid EAN, when placed within a micrometer-spaced enclosure, forms an ordered phase, which is similar to a liquid crystal. The peculiarity of this phase is that the cations do not have a predominant orientation. Other features of this phase that are typical for liquid crystal phases are the changed local and translational dynamics in comparison with the isotropic state and slow transformation occurring under the action of an external magnetic field.