Time-resolved study of acetyl radical in zeolite NaY by step-scan FT-IR spectroscopy

Step-scan FT-infrared spectroscopy of l-naphthyl acetate and pinacolone photodissociation in zeolite NaY revealed a transient at 2125 cm(-1) assigned to acetyl radical. Comparison of the intensities of transient and final product absorptions, 2-acetyl-1-naphthol in the case of naphthyl acetate and acetaldehyde for pinacolone, indicates that the acetyl radical represents the main, and probably only, reaction channel. The decay of the radical at room temperature is best described by a single-exponential law with a lifetime of 71 +/- 15 mu s (1-napthyl acetate) and 315 +/- 30 mu s (pinacolone). This constitutes the first detection and kinetic study of a small transient radical in a zeolite. The kinetic result is interpreted in terms of complete separation of the photogenerated pairs from the parent supercage, followed by random walks in subspaces of the zeolite lattice imposed by the much less mobile precursor molecules. These force the geminate radicals to react and thereby contribute to the high selectivity of these photoreactions.