The fact that the number of HBs between the macrocycle and the rest of the rotaxane remains At the same time, with the rupture of the π -π interactions and of the HBs, the binding between the axle and macrocycle becomes less constrained, and the entropic term becomes more favorable (minima of the blue line in Fig. , top). The blue profile of the entropic term is found rather similar to that of the FES (black), indicating that the behavior of such rotaxane is largely controlled by entropy in such conditions.