Here we report the crystal structures of dicationic ionic liquids (ILs) with both modified cation and anion moieties and discuss the influence of the “supramolecular ionic liquid architecture” that these subtle changes incur. The four dicationic ILs, 1,8-bis(1-methylimidazolium-3-yl)octane bromide (1), 1,8-bis(1,2-dimethylimidazolium-3-yl)octane bromide (2), 1,8-bis(1,2-dimethylimidazolium-3-yl)octane tetrafluoroborate (3) and 1,12-bis(1-methylimidazolium-3-yl)dodecane bromide (4) were prepared using established literature methods. Single crystals of the materials were grown (as solvates for 1·2H2O and 4·1.2(C7H8)) and the solid-state structural arrangements determined by single crystal X-ray diffraction.
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