Supramolecular Subphthalocyanine Cage as Catalytic Container for the Functionalization of Fullerenes in Water

Abstract Herein we report the first example of a supramolecular cage that works as a catalytic molecular reactor to perform transformations over fullerenes in aqueous medium. Taking advantage of the ability of metallo–organic Pd(II)‐subphthalocyanine (SubPc) capsules to form stable host:guest complexes with C 60 , we have prepared a water‐soluble cage that provides a hydrophobic environment for conducting cycloadditions over encapsulated C 60 , namely, Diels–Alder reactions with anthracene. Indeed, the presence of catalytic amounts of SubPc cage dissolved in water promotes co‐encapsulation of insoluble C 60 and anthracene substrates, allowing the reaction to occur inside the cavity under mild conditions. The lower stability of the host:guest complex with the resulting C 60 cycloadduct facilitates its displacement by pristine C 60 , which grants catalytic turnover. Moreover, bis‐addition compounds are regioselectively formed inside the cage when using excess anthracene.