Small-Angle X-ray Scattering Studies of Liquid Crystalline 1-Alkyl-3-methylimidazolium Salts

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Abstract

A series of long-chain 1-alkyl-3-methylimidazolium salts ([Cn−mim]X, n = 12−18) containing the anions, chloride, bromide, trifluoromethanesulfonate (OTf), and bis(trifluoromethanesulfonyl)imide (TFI), have been synthesized and characterized. The salts have amphiphilic characteristics, and the thermotropic phase behavior of these salts and the analogous tetrafluoroborate salt has been investigated by variable temperature small-angle X-ray scattering, polarizing optical microscopy, and differential scanning calorimetry. The salts form lamellar, sheetlike arrays in the crystalline phase and an enantiomeric smectic liquid crystalline phase at higher temperatures, except for the salts containing the bis(trifluoromethanesulfonyl)imide anion which melt directly to form isotropic liquids. The nature of the anion influences the size of the interlayer spacing in both the crystal and in the mesophase. The interlayer spacing in the mesophase is largest for the anions with the greatest ability to form a three-dimensional hydrogen-bonding lattice, following the order [TFI]- < [OTf]- < [BF4]- < Br- < Cl-.

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