Some novel liquid crystalline phthalocyanines form extraordinary supramolecular structures. These include an amphiphilic phthalocyanine displaying lyotropic as well as thermotropic behavior, a chiral phthalocyanine forming a helical mesophase at room temperature, and a liquid crystalline phthalocyanine containing crown ether rings which forms large columnar aggregates in solution. All these compounds can be used to prepare Langmuir-Blodgett films with varying arrangements of the molecules.