All the parameters employed for these kinetic studies are reported in the SI per each simulated system. Furthermore, complete details on the WT-MetaD and infrequent WT-MetaD input files used herein are also available at: GMPavanLab/MIMs (this link will be replaced with a definitive Zenodo archive upon acceptance of the final version of this paper). adsorption of fumaramide [2] For each system, we ran a minimum of 1.5 µs, allowing us to record multiple shuttling events across stations. For the calculation of the shuttling rates in 1 from bound to unbound we ran 25 infrequent WT-MetaD simulations, starting from the bounded state and biasing the distance between the center of geometry of the ring and the center of geometry of the closest benzimidazolium (d1, CV1) and the distance (d benz-benz , CV2) between the two benzene rings of the dibenzo [24]crown-8 ether macrocycle. Each run ends when CV1 falls in basin D (see 2D-FES in fig. of the main paper). In ACN, the bias has been added every 20 ps using Gaussians of initial height 1 kJ/mol, width of 0.1 nm and 0.05 nm for CV1 and CV2, respectively, and a bias factor of 20. In CHCl 3 and DCM, the bias has been added every 50 ps, using Gaussians of initial height 2 kJ/mol, a width of 0.1 nm and 0.05 nm for CV1 and CV2, respectively, and a bias factor of 45. In DMSO, the bias has been added every S4