Ordered Architectures of a Soluble Hexa-peri-hexabenzocoronene−Pyrene Dyad:  Thermotropic Bulk Properties and Nanoscale Phase Segregation at Surfaces

An alkylated hexa-peri-hexabenzocoronene with a covalently tethered pyrene unit serves as a model to study self-assembling discotic pi-system dyads both in the bulk and at a surface. Wide-angle X-ray scattering, polarized light microscopy, and differential scanning calorimetry revealed bulk self-assembly into columnar structures. Relative to a control without a tethered pyrene, the new dyad exhibits a more ordered columnar phase at room temperature but with dramatically lowered isotropization temperature, facilitating homeotropic alignment. These two features are important for processing such materials into molecular electronic devices, e.g., photovoltaic diodes. Scanning tunneling microscopy at a solution-solid interface revealed uniform nanoscale segregation of the large from the small pi-systems, leading to a well-defined two-dimensional crystalline monolayer, the likes of which may be employed in the future to study intramolecular electron transfer processes at surfaces, on the molecular scale.