A C60-ionic liquid hybrid has been covalently linked to three different solid supports, namely amorphous silica, SBA-15 and Fe2O3@SiO2, and the resulting materials have been employed as covalently supported ionic liquid phases (cSILP) in order to immobilize and stabilize palladium nanoparticles (PdNPs). These novel hybrid materials are based on a sort of "matryoshka" system (PdNPs@imidazolium-salt@C60@support) in which the imidazolium-based moieties have not been directly linked to the surface of the support, but they are present in an octopus-like spatial arrangement on the uniformly surface-distributed fullerenes. These materials have been fully characterized and successfully employed as catalysts in C-C bond forming reactions showing, in the case of Suzuki cross-coupling, an outstanding catalytic activity both under classical heating and by irradiating with microwaves. Turn-over frequencies (TOFs) of up to 3640000 h-1 have been achieved and the silica-based catalyst showed full recyclability even after 10 cycles.
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