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Attraction between Like Charged Ions in Ionic Liquids: Unveiling the Enigma of Tetracyanoborate Anions
Kateryna Goloviznina1, Eduards Bakis2, Frederik Philippi3
1Physicochimie des Électrolytes et Nanosystèmes Interfaciaux (PHENIX), Sorbonne Université and CNRS, F-75005 Paris, France.
Abstract:
Intermolecular interactions in ionic liquids are mainly governed by Coulombic forces. Attraction between cations has been previously observed and was attributed to dispersion interactions between nonpolar moieties, hydrogen bonding, or π stacking. In this study, we present the intriguing behavior of tetracyanoborate anions in ionic liquids that, unlike their dicyanamide and tricyanomethanide counterparts, form dimers in both solid and liquid phases. A joint simulation and experimental study uncovers the origin of such anion-anion attraction: stabilization by induction and dispersion forces between several cyano groups, which is strong enough to overcome electrostatic repulsion. These findings open up new opportunities in the rational design of ionic liquids, where interactions between ions of the same charge can be controlled and fine-tuned by the presence of cyano groups.
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