Supra-aggregates of fiber-forming anisotropic molecules

In this paper, the self-organization of fiber-forming anisotropic molecules is inspected both theoretically and experimentally. In the first part, a theoretical model which extends the de Gennes theory of thin films to assemblies of strongly anisotropic molecules is reported. The model predicts that solid supported thin films made up of fiber-forming discotic molecules can grow with both tangential and radial arrangement of the fibers, respectively leading to the formation of compact and holed supra- aggregates. These last systems form according to the following picture. The tangential growth minimizes the number of unfavorable free ends but introduces elastic strain especially in the central region of the aggregate. To reduce the elastic strain, some molecules are displaced from the central region toward the periphery of the growing aggregate, producing a localized well. In the second part of the paper, we experimentally face the above issue by depositing a strongly anisotropic disk-shaped molecule (rhodamine 123) onto different solid substrates through a spin coating procedure. By employing scanning force microscopy (SFM), the formation of thermodynamically favored fiberlike supramolecules as well as of compact and holed submicron-sized supra-aggregates has been demonstrated. The observed phenomena have been found to depend on the interplay of different parameters such as molecular concentration, evaporation time, and substrate composition. As main features, both theory and experiments show that holed supra-aggregates are more stable beyond a critical aggregation size and that the formation of holes is favored at high supersaturation. The theory seems valuable in extending previous dewetting models developed for fluid films with isotropic interaction forces.