Nonlinear Dependence on Na+ Ions for the Binding Dynamics of Cucurbit[6]uril with the trans-1-Methyl-4-(4-hydroxystyryl)pyridinium Cation.

The binding dynamics of the trans-1-methyl-4-(4-hydroxystyryl)pyridinium cation (HSP+) to cucurbit[6]uril (CB[6]) in the presence of Na+ cations were studied to establish the effect of the relative concentrations of the system's components (HSP+, CB[6], and Na+) on these dynamics. The formation of the HSP+@CB[6] complex was temporally uncoupled from the photoisomerization of trans-HSP+, while a nonlinear effect of the Na+ cation concentration on the HSP+@CB[6] dynamics was observed. This nonlinearity is a consequence of Na+ having the opposite effect on the association and dissociation rate constants for the HSP+@CB[6] complex, creating a conceptual framework for using such nonlinearities to control multistep reactions in cucurbit[n]uril chemistry.