The Photolysis of Arenediazonium Salts in Solutions and Films: Quantum Efficiencies and Reactive Intermediates

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Abstract
Quantum efficiencies φdec for the photodecomposition by monochromatic light of a large number of both simple and commercially important arenediazonium salts have been determined at 293 K in 0.05 M aqueous sulphuric acid, 0.05 M acidic (HaSO,) ethanol and cellulose acetate film, enabling comparison (and discrimination) between results reported at various points in the literature for experiments performed in a single medium. The values of φdec derived for solutions yield good Hammett plots, indicating a sensitivity of φdec towards the electronic effect of substituent groups. Very little such elfect was, however, apparent for a series of arenediazonium salts in cellulose acetate film. Variation of the irradiation wavelength within the absorption band of the arenediazonium salts was found to produce no significant change in φdec in aqueous acid solution. E.s.r. signals due to the Ar+ species formed during the photoreaction have been observed on photoirradiation of cellulose acetate films of 4-dialkylamino-substituted arenediazonium salts at 77 K in the cavity of an e.s.r. spectrometer: these appear at field positions typical of a triplet state species.

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