Very short NMR relaxation times of anions in ionic liquids: New pulse sequence to eliminate the acoustic ringing

Abstract

NMR relaxation processes of anions were studied in two neat imidazolium-based room temperature ionic liquids (RTILs) 1-decyl-3-methyl-imidazolium bromide- and chloride. The spin–lattice and spin–spin relaxations of 81Br and 35Cl nuclei were found to be extremely fast due to very strong quadrupolar interactions. The determined relaxation rates are comparable with those observed in the solids or in some critical organic solute/water/salt systems. In order to eliminate the acoustic ringing of the probe-head during relaxation times measurements the novel pulse sequence has been devised. It is based on the conventional inversion recovery pulse sequence, however, instead of the last 90° pulse the subsequence of three 90° pulses applied along axes to fulfill the phase cycling condition is used. Using this pulse sequence it was possible to measure T1 for both studied nuclei. The viscosity measurements have been carried out and the rotational correlation times were calculated. The effective 35Cl quadrupolar coupling constant was found to be almost one order lower than that for 81Br, i.e. 1.8MHz and 16.0MHz, respectively. Taking into account the facts that the ratio of (Q(35Cl)/Q(81Br))2≈0.1 and EFG tensors on the anions are quite similar, analogous structural organizations are expected for both RTILs. The observed T1/T2 (1.27–1.44) ratios were found to be not sufficiently high to confirm the presence of long-living (on the time scale of ⩾10−8s) mesoscopic structures or heterogeneities in the studied neat ionic liquids.