Redox-switchable host-guest complexes of metallocenes and [8]cycloparaphenylene

The cycloparaphenylene (CPP) nanocarbons are an appealing family of macrocyclic organic semiconductors with size-tunable structures and unique optoelectronic properties, which can be further modulated by complexation with guest molecules. While many π-π-stabilized CPP-fullerene host-guest complexes are known, CPPs can also host polycyclic guests stabilized by aromatic CH-π interactions. Here we combine experimental and computational results to report that CH-π interactions can also be tapped to include redox-active metallocene guests in [8]cycloparaphenylene ([8]CPP). Oxidation of a metallocene guest is accompanied by an increase in binding affinity and tilt angle. Crystallographically determined solid-state structures reveal CH-π interactions in the ferrocene complex (Fc⊂[8]CPP) and additional π-π interactions in the cobaltocenium complex (CoCp₂⁺⊂[8]CPP). Functionalizing Fc with oxygen-bearing side chains also improves complex stability to a similar extent as oxidation, due to the formation of CH-O hydrogen bonds with the host's p-phenylene units. This work shows that CH-π bonding can be generalized as a driving force for CPP host-guest complexes and combined with other supramolecular forces to enhance stability. Owing to their semiconducting nature, amenability to functionalization, and reversible redox-dependent behavior, the [8]CPP-metallocene host-guest complexes may expand the library of synthons available for designing bespoke nanoelectronics and artificial molecular machines.