[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 via 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 (ΔG‡ ca. 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.

This article is Open Access

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