Attraction between Like Charged Ions in Ionic Liquids: Unveiling the Enigma of Tetracyanoborate Anions

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...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2024-01, Vol.15 (1), p.248-253
Main Authors: Goloviznina, Kateryna, Bakis, Eduards, Philippi, Frederik, Scaglione, Nicolas, Rekis, Toms, Laimina, Laura, Costa Gomes, Margarida, Padua, Agilio
Format: Article
Language:English
Subjects:
Physical Insights into Quantum Phenomena and Function
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Summary: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.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.3c02983