This paper reports unique and unusual formations of columnar liquid crystals and organogels by self-assembling discotic molecules, which are composed of an aromatic hexaazatriphenylene (HAT) core and
six flexible aromatic side chains. In HAT derivatives 3a, with 4‘-(N,N-diphenylamino)biphenyl-4-yl chains,
3b, with 4‘-[N-(2-naphthyl)-N-phenylamino]biphenyl-4-yl chains, and 3c, with 4‘-phenoxybiphenyl-4-yl
chains, the two-dimensional hexagonal packings can be created by their self-assembling in the liquid
crystalline phase, which were characterized by polarizing optical microscopy, differential scanning
calorimetry, and X-ray diffraction analysis. In certain solvents, HAT molecules 3a−c can form the viscoelastic
fluid organogels, in which one-dimensional aggregates composed of the HAT molecules are self-assembled
and entangled into three-dimensional network structures. The organogel structures were analyzed by
scanning electron microscopy observation, 1H NMR, UV−vis, and circular dichroism spectroscopy. In
contrast to 3a−c, none of the liquid crystalline and organogel phases could be formed from 3d and 3e with
short aromatic side chains including a phenylene spacer, and 3f (except a few specific solutions) and 3g
without terminal diarylamino and phenoxy groups. In 3a−c, the aromatic side chains with terminal
flexible groups make up soft regions that cooperatively stabilize the liquid crystalline and organogel
supramolecular structures together with the hard regions of the hexaazatriphenylene core.