Hierarchical Fullerene Assembly: Seeded Coprecipitation and Electric Field Directed Assembly

Hierarchical C₆₀ colloidal films are assembled from nanoscale to macroscale. Fullerene molecular crystals are grown via seeded cosolvent precipitation with mixed solvent [tetrahydronaphthalene (THN)/trimethylpyridine (TMP)] and antisolvent 2‐propanol. The fullerene solutions are aged under illumination, which due to the presence of TMP reduces the free monomer concentration through fullerene aggregation into nanoparticles. The nanoparticles seed the growth of monodisperse fullerene colloids on injection into the antisolvent. Diverse colloidal morphologies are prepared as a function of injection volume and fullerene solution concentration. The high fullerene solubility of THN enables C₆₀ colloids to be prepared in quantities sufficient for assembly (5 × 10⁸). Electric fields are applied to colloidal C₆₀ platelets confined to two dimensions. The particles assemble under dipolar forces, dielectrophoretic forces, and electrohydrodynamic flows. Frequency‐dependent phase transitions occur at the critical Maxwell–Wagner crossover frequency, where the effective polarizability of the particles in the medium is substantially reduced. Structures form as a function of field strength, frequency, and confinement including hexagonal, oblique, string fluid, coexistent hexagonal‐rhombic, and tetratic.