Thermotropic phase behavior of trialkyl cyclohexanetriamides

The thermotropic phase behavior of symmetric cyclohexanetriamides carrying various linear and branched alkyl chains was investigated using calorimetry, microscopy, solid-state NMR, dielectric relaxation spectroscopy, and X-ray scattering techniques. Cyclohexanetriamides carrying C₆ or longer linear alkyl chains formed columnar plastic phases with a pseudocentered rectangular lattice. Those with C₈ or longer alkyl chain also showed a nematic liquid crystalline phase. Cyclohexanetriamides carrying branched octyl chains displayed columnar phases with rectangular lattices, except for the triamide with the highly branched tetramethylbutyl group. The occurrence of less symmetrical columnar phases is ascribed to the mode of stacking of cyclohexanetriamides which leads to noncylindrical columns. Dielectric relaxation spectra also featured highly cooperative relaxation processes related to reorientation of the macrodipolar columns in the mesophase, showing the potential of these molecules as building blocks in responsive materials.