Dicyanamide Salts that Adopt Smectic, Columnar, or Bicontinuous Cubic Liquid-Crystalline Mesophases.

Although dicyanamide (i.e., [N(CN)2 ]- ) has been commonly used to obtain low-viscosity, halogen-free, room-temperature ionic liquids, liquid-crystalline salts containing such anions have remained virtually unexplored. Here we report a series of amphiphilic dicyanamide salts that, depending on their structures and compositions, adopt smectic, columnar, or bicontinuous cubic thermotropic liquid-crystalline mesophases, even at room temperature in some cases. Their thermal properties were explored by polarized light optical microscopy, differential scanning calorimetry, thermogravimetric analysis (including evolved gas analysis), and variable-temperature synchrotron X-ray diffraction. Comparison of the thermal phase characteristics of these new liquid-crystalline salts featuring "V-shaped" [N(CN)2 ]- anions with those of structural analogues containing [SCN]- , [BF4 ]- , [PF6 ]- , or [CF3 SO3 ]- anions indicated that not only the size of the counterion but also its shape should be considered in the development of mesomorphic salts. Collectively, these discoveries may be expected to facilitate the design of thermotropic ionic liquid crystals that form inverted-type bicontinuous cubic and other sophisticated liquid-crystalline phases.