Hierarchically Organized Honeycomb Films Based on the Self-Assembly of Fulleromonodendrons

We report the preparation of honeycomb structures (HCSs) by the breath figure method with high contents of fullerene C60 (>60 wt %) with a series of monosubstituted C60 derivatives (fulleromonodendrons) terminated with oligo-poly(ethylene oxide) (o-PEO) chains. It was found that a fulleromonodendron with two terminal o-PEO chains substituted at the 2,4-position of the benzene ring is the best candidate for the preparation of HCSs. The C60-based HCSs have hierarchically organized pores locating both on the film surface and inside the film. After blending with branched or linear polystyrene, the surface morphology and the internal structure of the film were further optimized. In addition, new functions such as photoluminescence have been introduced to the film. On the basis of the investigation of the aggregation behavior of the fulleromonodendron in CHCl3 as well as the exploration of the molecular organization and optical and electrochemical properties of the HCSs, the mechanism behind the film formation has been deduced. These hierarchically organized porous films with unprecedentedly high content of fullerene C60 may find applications in sensors, catalysis, and template synthesis of functional materials.