Coupled to the translational motion of the macrocycle, such a rotational degree of freedom of the macrocycle around the central fullerene and the main rotaxane axle demonstrates how this rotaxane exhibits multi-layered, complex dynamics characterized by multiple degrees of freedom and motion types. The translational motion of the macrocycle is accompanied by an entropic cost that is required to have the macrocycle to pass through the flexible linkers (already observed in similar [2]Rotaxanes with flexible linkers ). The presence of ten clear periodic minima indicates that the motion is step-wise, determined by the possible π-stacking of [10]CPP and fullerene benzene rings. We also employed a clustering analysis (Probabilistic Analysis of Molecular Motifs 84 ) to capture the transitions between these angular minima along the MD simulations, which allowed us to characterize the kinetics of the step-by-step CPP rotation around the fullerene. We thus estimated a mean residence time for the CPP in each minimum configuration as ∼0.1 ns, which reveals that such step-wise macrocycle rotation is fast in these conditions. This combination of PC and clustering analysis provides a further, useful strategy to characterize the complex dynamics in these systems, providing in this case a quantitative proof of the high-rotational degrees of freedom of the macrocycle in this bound state, and demonstrating how such bound state correspond to a highly entropically favored minimum energy configuration (Fig. : deep black and blue minima at d = 0 nm).