Effect of cyclodextrin encapsulation on the photocyclization of diphenylamine: Cavity imposed restriction on the reaction rate

Abstract

The kinetics of the photocyclization of diphenylamine (DPA) to carbazole (CAZL) has been studied fluorometrically in air-equilibrated aqueous solution as well as in constrained microheterogeneous media provided by [alpha]-, [beta]-, and [gamma]- cyclodextrins (CDs). It is observed that the fluorophore is embedded within the CD cavities without any alteration of the overall reaction quantum yield in the different environments. However, the rate of the photoreaction is modified remarkably within the CD environments. A restriction on the intramolecular rotation of the phenyl planes of DPA, imposed by the steric rigidity within the CD cavities, has been ascribed to be responsible for the suppression of the reaction rates within the CD environments. A semi-empirical (AM1) calculation gives the molecular dimension of the substrate and corroborates the proposition from a consideration of the cavity size of the different cyclodextrins.