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Cluster formation through hydrogen bond bridges across chloride anions in a hydroxyl-functionalized ionic liquid.
Several recent studies of hydroxyl-functionalized ionic liquids (ILs) have shown that cation-cation interactions can be dominating these materials at the molecular level when the anion involved is weakly interacting. The hydrogen bonds between the like ions led to the formation of interesting chain-like, ring-like, or distinct dimeric (i.e. two ion pairs) supermolecular clusters. In the present work, vibrational spectroscopy (ATR-IR and Raman) and quantum chemical theory (DFT) of the hydroxyl-functionalized imidazolium ionic liquid C2OHmimCl indicate that anion-cation hydrogen bonding interactions are dominating and lead to the formation of distinct dimeric ion pair clusters. In this arrangement the Cl- anions function as a bridge between the cations by establishing bifurcated hydrogen bonds with the OH group of one cation and the C(2)-H of another cation. Cation-cation interactions, on the other hand, do not play a significant role in the observed clusters.
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