Photochromism in Cucurbit[8]uril Cavity: Inhibition of Hydrolysis and Modification of the Rate of Merocyanine–Spiropyran Transformations

Abstract

The effect of inclusion complex formation on the photochromic behavior of a spirobenzopyran dye and its merocyanine isomer was studied in aqueous solution using cucurbit[8]uril (CB8) as a host. The merocyanine (MC) and protonated merocyanine (MCH(+)) were the most stable forms both in water and inside the cavity of CB8. The equilibrium constant of 1:1 complexation with CB8 was found to be 1.7 × 10(5) and 2.0 × 10(6) M(-1) for the former and latter species, respectively. The encapsulation led to significant change in the rate of the photoinduced and thermal photochromic transformations and hindered the hydrolysis of MC. The effect of CB8 on the reaction kinetics strongly altered with pH. The transition from the spiropyran form to trans-MC in a thermal reaction had 33 kJ mol(-1) lower activation energy and more than 5 orders of magnitude smaller Arrhenius pre-exponential factor in CB8 than in water.