Glassy Porphyrin/C60 Composites: Morphological Engineering of C60 Fullerene with Liquefied Porphyrins

Morphological control of C60 fullerene using liquefied porphyrins (1 and 2) as the host matrices was explored. Slow evaporation of the solvent of the equimolar mixture of porphyrin and C60 in toluene afforded the porphyrin/C60 composite with a 3:1 molar ratio. The stoichiometric binding behaviors suggest that specific porphyrin-C60 interactions operate the formation of the porphyrin/C60 composites, as corroborated by spectroscopic and thermal properties, and glazing-incidence wide-angle X-ray diffraction. Under the bulk conditions, the conventional thermodynamic advantage of multiple binding cooperativity for molecular recognition is unlikely to explain the stoichiometric binding behaviors. Instead, we propose a size-matching effect on the porphyrin-C60 interaction in the bulk porphyrin matrices, i.e., "supramolecular solvation". The glassy nature of the porphyrin matrices was transmitted to C60 through the specific interaction, and the porphyrin/C60 composites adopted glassy states at room temperature.