Fluorescent J-type aggregates and thermotropic columnar mesophases of perylene bisimide dyes

A series of perylene tetracarboxylic acid bisimides 3a-e bearing 3,4,5-tridodecyloxyphenyl substituents on the imide N atoms and zero, two, or four phenoxy-type substituents in the bay positions of the perylene core were synthesized. From investigations of their spectroscopic properties and aggregation behavior in low-polarity solvents by absorption and fluorescence optical spectroscopy, not only were these compounds found to form fluorescent J-type aggregates, but also binding constants for aggregation could be derived which reflect the number and steric demand of the phenoxy substituents for bisimides 3a-d. In the pristine state, 3a-d form thermotropic hexagonal columnar mesophases which exist over a broad temperature range from below -30 degrees C to over 300 degrees C. For the tetraphenoxy-substituted compound 3e, however, a layered crystalline structure was found. This difference in behavior can be explained by the concept of microphase segregation of the aromatic cores of the molecules and the alkyl chains at the periphery. The high stability and bright fluorescence of the mesophase of several of the compounds make them promising for applications as polarizers or components in (opto)electronic devices.