Development of cation/anion "interaction" scales for ionic liquids through ESI-MS measurements

Electrospray ionization mass spectrometry applied to ionic liquids allowed the study of loosely bonded supramolecules, originating from these organic salts. Based on the observation that ionic liquids formed cationic C(q+1)X(q)](+) and anionic C(q)X(q+1)](-) supramolecular aggregates, we have investigated mixed networks, formed by different cations coordinated to a selected anion or by different anions bonded to a given cation, i.e., C1...X...C2](+) and X1...C...X2](-), with the aim to build a scale of the cation-anion interaction strength. The qualitative order of intrinsic bond strength to Br- was found to be the following: emim](+) > bmim](+) > mor1,2](+) > hmim]+ > omim](+) > mor1,4](+) > bupy](+) > bpyrr](+) > picol](+) > bm(2)im](+) > TBA](+). Similarly, the interaction energies to 1-butyl-3-methylimidazolium (bmim) species envisaged two classes of anions: species tightly coordinated to the cationic moiety that include CF3COO(-), Br(-), N(CN)2(-), and BF4(-) and anions loosely interacting with the alkylimidazolium species such as OTf(-), PF6(-), and Tf2N(-).