Observation of shuttling on the one-second timescale in a [10]cycloparaphenylene/C ₆₀ [2]catenane

[2]Catenanes comprising two identical binding sites are an excellent platform to study the kinetics of non-covalent interactions. In this work, we show that the "shuttling" of the [10]CPP nanohoop between two identical fullerene bis-adduct binding sites occurs with regioisomer-dependent rates of 1-5 s^-1 at room temperature, placing these among the slowest π-π and dispersion-based shuttling processes reported to date. The catenanes were accessed <i>via</i> Glaser-Eglinton macrocyclization from fullerene bis-adduct precursors, which were purified by extensive recycling chromatography, and characterized by variable-temperature ¹H NMR spectroscopy. Molecular dynamic simulations employing well-tempered metadynamics closely reproduce the experimental activation barrier (Δ<i>G</i> ^‡ <i>ca.</i> 70 kJ mol^-1), offering insight into the nanohoop's motion and metastable states along the shuttling pathway. The kinetic data were further complemented by thermodynamic binding studies between [10]CPP and different fullerene bis-adduct regioisomers. These findings expand our understanding of the kinetics and thermodynamics of concave/convex π-π interactions and will inform the design of future mechanically interlocked machines and 2D materials with slow response to external stimuli.