Fullerene Building Blocks with Tailor-Made Solubility and New Insights into Their Hierarchical Self-Assembly

Abstract

Herein, the synthesis of fullerene derivatives with adjustable polarities and lyotropic aggregation properties is reported. The polarity range spans from superhydrophobic to hydrophilic, while simultaneously providing a further reactive position with a view to graft them onto other materials. The synthetic strategy relies on a selective protection with an isoxazoline moiety. The remaining octahedral positions were further functionalized with the desired groups to tune their solubility, yielding mixed [5:1] hexakisadducts. The subsequent deprotection by clean photolytic reaction led to fullerene pentakisadducts with an incomplete octahedral addition pattern, which are useful forerunners for the synthesis of building blocks. Their hydrophobic/hydrophilic behavior has been characterized both in solution and surface through octanol/water partition coefficients (log P) and contact angle measurements. Furthermore, these derivatives can form supramolecular constructions which have been studied by dynamic light scattering (DLS) and cryo-TEM.