Studies of the thermotropic mesophase behaviour exhibited by a highly asymmetric tetrabenzotriazaporphyrin derivative

Abstract

The thermotropic mesophase behaviour of an asymmetrically shaped and highly substituted tetrabenzotriazaporphyrin (TBTAP) derivative has been studied by optical microscopy, DSC and X-ray diffraction. The TBTAP macrocycle differs from the more common phthalocyanine ring system by the substitution of a methine for a nitrogen at one meso-position. The TBTAP core was substituted with a single heptadecyl chain at this meso-position and four neopentyl groups were statistically distributed around the peripheral benzene rings. In contrast to an earlier study of this system which described the structure of the mesophase as discotic lamellar, detailed X-ray diffraction study indicates that the TBTAP derivative forms a disordered hexagonal columnar mesophase (Col_hd), with a weak tendency towards antiparallel orientation of neighbouring molecules observed in the form of a weak pseudo-centred rectangular packing.