Amphotropic Ionic Liquid Crystals with Low Order Parameters

Received October 6, 2003. Revised Manuscript ... Georgetown University. (1) Diehl, P. .... of CH3CN (Figures 5 and 6) confirm that the low-angle peaks...
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Chem. Mater. 2004, 16, 2101-2106

2101

Amphotropic Ionic Liquid Crystals with Low Order Parameters† G. A. Nagana Gowda,‡ Hui Chen,§ C. L. Khetrapal,‡ and Richard G. Weiss*,§ Center of Biomedical Magnetic Resonance, Sanjay Gandhi Post Graduate Institute of Medical Sciences, Lucknow, India, and Department of Chemistry, Georgetown University, Washington, D.C. 20057-1227 Received October 6, 2003. Revised Manuscript Received April 7, 2004

Methyl-tri-n-decylphosphonium salts (1P10A, where the counterion A is NO3- or the hydrate of bromide, Br-‚H2O) have been shown to exhibit unique liquid-crystalline properties as neat compounds and with high concentrations (up to 20 wt %) of a small organic molecule, acetonitrile. These results indicate dual thermotropic-lyotropic (i.e., amphotropic) behavior. Optical micrographs of salts with even small amounts of acetonitrile are oily streak patterns. The low-angle peaks in X-ray diffractograms characteristic of the lamellar spacings in the smectic A phases of the neat salts are broadened but do not change their positions appreciably as the concentration of added acetonitrile is increased. The liquid-crystalline phases of both salts become oriented in strong magnetic fields. As a result, NMR experiments with the nitrate salt exhibited only one type of orientation for acetonitrile at concentrations up to ca. 10 wt %. However, two types of orientations with opposite signs of the order parameter were detected in the Br-‚H2O salt at