Intrazeolite photochemistry. IV. Studies of carbonyl photochemistry on the hydrophobic zeolite Silicalite using time-resolved diffuse reflectance techniques

Transient absorption and luminescence from aromatic ketone triplets (xanthone, acetophenone, butyrophenone, valerophenone, p-methoxyacetophenone, β-phenyl-p-methoxypropiophenone and benzil) supported on the hydrophobic zeolite Silicalite have been obtained by time-resolved diffuse reflectance laser flash photolysis. These experiments were aimed at establishing the usefulness of this technique for studies of zeolite supported photoreactions. While the transient spectral properties can be used to examine the properties of the supporting media, the decays of the signals frequently follow complex kinetic behaviour. The decays for such heterogeneous systems cannot be easily fit to clean first or second order kinetics and are thought to be a mixture of several first order decays arising from triplets in different inclusion and adsorption sites. Evidence is presented for close-packing of the aromatic substrates and for triplet lifetime enhancement. Although the triplet spectrum of included benzil shows evidence for considerable axial freedom, the results for β-phenylpropiophenones indicate that other types of motion are restricted for included ketones. It is also found that the rate of the Norrish Type II reactions of valerophenone and butyrophenone supported on Silicalite are decreased with respect to the rates in solution.