Molecular models and computer simulations are useful to this end, as they may provide a direct and detailed viewpoint on the atomistic/molecular mechanisms that regulate the dynamics of MIMs. Molecular Dynamics (MD) simulations have been used, for example, to investigate the effect of the solvent and the surrounding environment modulate the thermodynamics of various rotaxanes. However, in many MIMs the shuttling occurs on timescales that largely exceed those accessible via classical atomistic MD simulations. Enhanced sampling techniques (such as, e.g., metadynamics, adaptive bias force, etc.) are useful in such cases, allowing to investigate rare transition events that occur on experimentally-relevant timescales at atomistic/sub-molecular resolution rare. For example, metadynamics (MetaD) simulations have been recently used to investigate the dynamics of monomer exchange in supramolecular polymers or the innate guest exchange dynamics in-and-out the cavity of a coordination cage, as well as the motion and dynamic behaviors of supramolecular systems (e.g., nanoparticles, tubules) in out-of-equilibrium conditions or under the effect of an external stimulus. Offering the opportunity to study molecular motion events occurring on long timescales at atomistic resolution and providing precious insights on the key steps or factors controlling them, these approaches are well suited also to study the dynamics of MIMs such as, e.g., rotaxanes and molecular shuttles.