Structural Motifs in Cold Ternary Ion Complexes of Hydroxyl-Functionalized Ionic Liquids: Isolating the Role of...

We address the competition between intermolecular forces underlying the recent observation that ionic liquids (ILs) with a hydroxyl-functionalized cation can form domains with attractive interactions between the nominally repulsive positively charged constituents. Here we show that this behavior is present even in the isolated ternary (HEMIm⁺)₂NTf₂^- complex (HEMIm⁺ = 1-(2-hydroxyethyl)-3-methylimidazolium) cooled to about 35 K in a photodissociation mass spectrometer. Of the three isomers isolated by double resonance techniques, one is identified to exhibit direct contact between the cations. This linkage involves a cooperative H-bond wherein the OH group on one cation binds to the OH group on the other, which then attaches to the basic N atom of the anion. Formation of this motif comes at the expense of the usually dominant interaction of the acidic C₍₂₎H group on the Im ring with molecular anions, as evidenced by isomer-dependent shifts in the C₍₂₎H vibrational fundamentals.