The Influence of Deuterium Isotope Effects on Structural Rearrangements, Ensemble Equilibria, and Hydrogen Bonding in Protic Ionic Liquids

We report strong isotope effects for the protic ionic liquid triethylammonium methanesulfonate [TEA][OMs] by means of deuterium solid‐state NMR spectroscopy covering broad temperature ranges from 65 K to 313 K. Both isotopically labelled PILs differ in non‐deuterated and fully deuterated ethyl groups of the triethyl ammonium cations. The N−D bond of both cations is used as sensitive probe for hydrogen bonding and structural ordering. The (2)H NMR line shape analysis provides the deuteron quadrupole coupling constants and the characteristics of a broad heterogeneous phase with simultaneously present static and mobile states indicating plastic crystal behavior. The temperatures where both states are equally populated differ by about 80 K for the two PILs, showing that deuteration of the ethyl groups in the trialkylammonium cations tremendously shifts the equilibrium towards the static state. In addition, it leads to a significant less cooperative transition, associated with a significantly reduced standard molar transition entropy.