For each simulated host-guest complex, encapsulation free energies ( G), equilibrium constants K enc , expulsion free energy barriers ( G ‡ of f ), characteristic in-cavity residence times (t of f ), and the associated transition rates (k of f and k on ) estimated from the WT-MetaD simulations are reported. Comparing the encapsulation of the different isomers of 2 in the cavity of cage 1, either alone or when 1 also contains a co-guest (3 or 2 trans ), we could observe that in general the encapsulation of 2 cis is more favored than that of the 2 trans isomer in all studied cases (see Table and Figure ). The kinetic constants measured for the 2 trans encapsulation/expulsion in/out the cavity indicate that in all complexes the dynamics of the transitions are marginally affected by the presence of other guests in the cage (k of f and k on in the same orders of magnitude). On the other hand, the dynamics (and stability) of the 2 cis -complexes is more impacted by the presence of co-guests in the cage cavity, which are found to stabilize the 2 encapsulation in the cage cavity by ⇠ 2 4 orders of magnitude in the presence of 3 (lower k of f : more improbable/slower 2 expulsion out of cavity). Shown in Table , the estimated k of f for the expulsion of the 2 cis guest out from the cage cavity drops from ⇠ 7.1 ⇥ 10 1 s 1 , when only one 2 cis is present in the cavity of 1, to ⇠ 1 s 1 or ⇠ 5.9 ⇥ 10 2 s 1 , when 2 cis is co-encapsulated in the cavity of 1 with a 2 trans or with a 3 co-guest respectively. The k on , on the other hand, is found globally similar in all simulated cases (see Table ).