Fine-tuning supramolecular assemblies of fullerenes bearing long alkyl chains

Fine-tuning of the supramolecularly organized nanometer scale architectures of fullerene derivatives, fulleropyrrolidines substituted with a mono-, di-, or tri(n-hexadecyloxy)phenyl group is described. These synthetic fullerene derivatives possess one- (1), two- (2), or three- (3) long alkyl chains. The correlation between the number of alkyl chain multiplicity and the self-organized bilayer structures as the fundamental subunit as well as the superstructures formed in different solvents were investigated using microscopic and spectroscopic techniques. The fullerene derivatives studied formed interdigitated lamellar bilayer structures whose d spacing values, estimated by X-ray diffraction patterns, are 2.63 nm for 1, 3.50 nm for 2, and 4.28 nm for 3, respectively. There are the two differing intermolecular forces present due to C60 (sp2-carbons) or alkyl chains (sp3-carbons). Fullerene moieties always exhibit strong π–π interactions, while van der Waals interactions between alkyl chains can be altered by variation of their multiplicity. Substitution of three alkyl chains at the fullerene moiety (3) was the most effective method for stimulating polymorphism in its derivatives in different solvents.