Heteronuclear NOE Spectroscopy of Ionic Liquids

19F,1H HOESY experiments with three ionic liquids ([bmim]BF4, [bmim]PF6 and [emim]BF4) were run in two different solvents and neat. The results give preferred probabilities of presence and enable us to systematically study interactions between the cations and the anions in the ionic liquid phase by NMR spectroscopy. The influence of different solvents and of the presence or absence of air (i.e. oxygen) is discussed. This enabled us to substantially speed up the NMR experiments and to develop a more precise method for the investigation of liquid‐phase structures in ionic liquids. Short and painless: To study the interactions between the cations and the anions of ionic liquids, 19F,1H HOESY spectra are analyzed. Those experiments allowed a fast and precise means of determining preferred probabilities of presence. The method presents a routine alternative for the theoretical calculation of spatial distribution functions (SDF).