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Updated: Jun 16, 2026

From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
Solid and liquid charge-transfer complex formation between 1-methylnaphthalene and 1-alkyl-cyanopyridinium
Christopher Hardacre1, John D Holbrey, Claire L Mullan
1School of Chemistry and Chemical Engineering, The QUILL Centre, Queen's University Belfast, Belfast, UK BT9 5AG. c.hardacre@qub.ac.uk
Abstract:
Liquid charge-transfer (CT) complexes were observed to form on contacting electron-rich aromatics with electron withdrawing group appended 1-alkyl-4-cyanopyridinium ionic liquids (ILs). Cooling below the melting point of the ionic liquid resulted in crystallisation of ionic liquid from the complex for 2-cyano and 3-cyano pyridinium isomers and in the formation of a 1 : 1 IL : aromatic crystalline CT-complex with the 4-cyanopyridinium isomer. The liquid structure of a 1 : 1 mixture of 1-methyl-4-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide with 1-methylnaphthalene has been probed by neutron diffraction experiments and molecular dynamics simulations. A high degree of correlation between the experimental data and the simulations was found with a significant displacement of the anions from around the cation by the aromatic species and the resulting structure having pi-pi stacks between the cations and the aromatic.
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