Figure 6.

Molecular determinants of isomerization under confinement. (A) Relationship between isomerization rate (τ_trans–cis) and residence times (τ_off) of the guests inside the cage. (B) Relationship between τ_trans–cis and potential energy of host–guest interactions, ΔE_HG. (C) Relationship between τ_trans–cis and the number of contacts between the cage and the guest. (D) Relationship between τ_trans–cis and the volume (V) of guest molecules (see the SI Methods section for details on guest volume estimation). (E) Switching deceleration, τ_trans–cis/τ₀, as a function of the increase in guest volume (%ΔV_guest), in which τ₀ denotes isomerization time measured at the original volume of each guest. In plots A–E, the points correspond to guests AZB (black), M-AZB (green), F-AZB (cyan), and AZP (violet). (F) Average τ_trans–cis/τ₀ as a function of the average increase in guest volume (%ΔV_guest), obtained by averaging all data from plot E between systems with similar %ΔV_guest. The error bars indicate the standard deviation of %ΔV_guest and τ_trans–cis/τ₀ values. Inset: cartoon showing the volume of encapsulated M-AZB (green) inside the cage (white). The dashed lines in all plots are the logarithmic fit of the data.