A decomposition of the FES into ∆H and -T∆S contributions demonstrates that the global ∆G minimum in this system (corresponding to the macrocycle in central, bound configuration) is both enthalpically and entropically favored (see Fig. , bottom: black, blue and red curves minima at d = 0). This configuration allows maximizing the π stacking interaction between [10]CPP and the central C 60 fullerene, while at the same time preserving a high entropy in the system. In this bound state, the macrocycle can in fact easily rotate on the central fullerene, which guarantees a high number of degrees of freedom: this state thus corresponds to multiple possible rotationally-symmetric conformations for the ring on C 60 that are identical in energy while the macrocycle can "freely" rotate along the main axis of the dumbbell. We believe that in this respect, the match between the rigid [10]CPP macrocycle and the rigid C60-bisadduct binding site is rather unique.