Combining Proton and Electron Transfer to Modulate the Stability of Cucurbit[7]uril Complexes

(Ferrocenylmethyl)methylammonium (1H(+)) is an excellent cationic guest for inclusion complexation by the cucurbit[7]uril host. However, deprotonation of the guest leads to a decrease of 14.8 kJ mol(-1) in the overall stability of its inclusion complex, and one-electron oxidation of the guest's ferrocene residue further diminishes the complex stability by another 12.3 kJ mol(-1). Overall, guest deprotonation followed by its oxidation constitutes an accessible method to lower the equilibrium association constant for the CB7·1H(+) complex by more than 4 orders of magnitude.