A pH-Responsive Cu-Corrole-Based Cage That Reversibly Encapsulates Fullerene in a Shapeshifting Low-Symmetry Cavity

Artificial hosts combining chemical functionalities (recognition sites, stimuli responsive behaviour) in a low-symmetrical and guest-adaptive environment, are of major interest to better understand and mimic protein receptors. However, molecular cages are generally restricted to symmetrical cavities built from rigid subunits. For instance, porphyrin building blocks have a time-honoured role in the preparation of receptors and confined catalysts. Here, we introduce a new design for molecular cages based on corroles, the low symmetrical analogue of porphyrins, breathing life to desymmetrized cavities. A (CuIII)corrole complex was equipped with a shapeshifting cyclotriveratrylene (CTV) roof, via pH-responsive side arms. The latter enables the first metallocorrole-based cage CuIII(Hm-Cor) to reversibly bind fullerenes in a unique low-symmetry, conformationally adaptive, and pH-responsive cavity. Experimental and computational studies evidence flipping of the CTV roof upon fullerene binding, enabling structural reconfiguration of the host to optimise its size and shape to accommodate the guest. Such conformational changes also respond to the protonation of the cage’s side-arms. The reversible nature of this pH-responsive cavity allows fullerene release and reuse of the host. Beyond establishing a key precedent for preparation of caged metallocorroles, the present study provides a unique approach for the on-demand fullerene encapsulation in a low symmetry environment.