Synthesis and Characterization of Amphiphilic Fullerenes and Their Langmuir−Blodgett Films

We report here the synthesis and characterization of three amphiphilic fullerene derivatives and their Langmuir-Blodgett thin films. Two of the C(60) amphiphiles are mono-derivatives with a long alkyl chain terminated with either -COOH (2) or NH(2) (3) as the hydrophilic headgroup, and the third one (5) is designed to bear the same NH(2) group as 3 but with 10 additional hydrophobic alkyl chains grafted on the C(60) sphere (Scheme 1). These amphiphiles form stable, ordered monolayers at the air-water interface. The molecular packing at the air-water interface and the mean area per molecule are determined by pressure isotherms at room temperature. Hysteresis of pressure isotherms of side chain C(60) (5) shows complete reversibility upon compression and decompression, which suggests that side chains on the C(60) sphere inhibit formation of aggregates at the air-water interface. Comparative studies of all three amphiphiles allow us to better determine the interaction between C(60)'s and their self-assembly kinetics at the air-water interface. Monolayers of monoderivatized amphiphiles (2 and 3) were transferred successfully onto quartz substrates as Z-type multilayered Langmuir-Blodgett films, and monolayers of 5 were transferred as Y-type films. Detailed characterization of the multilayer films (Z-type deposition) prepared from amine-terminated C(60) (3) using X-ray and neutron reflectometry reveals staggering of C(60) spheres and a head-to-head (Y-type) structure presumably due to flipping and reattaching of C(60) amphiphiles to the previous underlying C(60) layer.