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Tuning cation-anion interactions in ionic liquids by changing the conformational flexibility of the cation.

Cation-anion interactions can be tuned via the degree of cation constraint. X-ray Photoelectron Spectroscopy (XPS) experiments reveal that anion-cation based interactions may be enhanced by introducing conformational restriction into the substituent chains of quaternary ammonium cations. A larger degree of charge-transfer was observed for the constrained [C8C1Pyrr](+) cation relative to the [N6,6,6,14](+) cation.