Competition between Cation–Solvent and Cation–Anion Interactions in Imidazolium Ionic Liquids with Polar Aprotic Solvents

The subtle interplay between ion solvation and association was analyzed in mixtures of imidazolium‐based ionic liquids (ILs) with polar aprotic solvents. A site‐specific pattern of cation–solvent and cation–anion interactions was disclosed by a careful analysis of the 1H and 13C NMR chemical shift dependence of the mixture composition. It was established that the less polar but more donating γ‐butyrolactone is more prone to establish H‐bonds with the imidazolium‐ring hydrogen atoms of the IL cations than propylene carbonate, particularly at the H2 site and at high dilutions xIL