All the model systems simulated herein were parametrized using the Generalized Amber Force Field (GAFF), except for the β dihedral angle of the formamidinimum [2]rotaxane (see SI). The partial charges for the atomistic models have been calculated using the RESP method, computed at Hartree-Fock (HF) level of theory, with 6-31G basis set, as implemented in Gaussian16. 87 AmberTools21 88 package was used for the parametrization of the systems. The solvent models were parametrized according to the virtualchemistry.org database. A proper amount of PF6 -ions have been added to neutralize the total charge of each system. All the systems simulated herein were initially subjected to energyminimization via the steepest-descent algorithm and then to a short (∼10 ns) equilibration in periodic NPT conditions (constant N: number of particles, P: pressure, T: temperature).