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Primary photochemical processes in aromatic molecules. Part 6.—The absorption spectra and acidity constants of phenoxyl radicals

Primary photochemical processes in aromatic molecules. Part 6.—The absorption spectra and acidity... PRIMARY PHOTOCHEMICAL PROCESSES IN AROMATIC MOLECULES PART 6.-TuTF, ABSORPTION SPECTRA AND ACIDITY CONSTANTS OF PHENOXYL RADICALS BY E. J. LAND, G. PORTER AND E. STRACHAN Dept. of Chemistry, Sheffield University Received 28th October, 1960 Phenoxyl radicals and their derivatives have been prepared by flash photolysis in gaseous and liquid systems, by chemical oxidation and by photolysis of rigid solutions. Their spectra have been recorded and the longer wavelength system, expected on theoret- ical grounds, has been observed. Investigations of the spectrum as a function of pH show that these radicals are very weak bases and that, contrary to the interpretations of some other workers, the spectra observed under all conditions except those of very high acidity are to be attributed to neutral unprotonated radicals. The photolysis of aromatic hydrocarbons having alkyl, amino or hydroxyl groups, gives rise to transient products which have been attributed to the benzyl, anilino and phenoxyl radicals respectively and to their derivatives. These absorp- tion spectra were first observed by Porter and Wright 1 in flash photolysis studies of aromatic vapours and were detected shortly afterwards by Norman and Porter 2 as trapped products of photolysis in glassy solutions at low temperatures. Whilst the benzyl http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Transactions of the Faraday Society Royal Society of Chemistry

Primary photochemical processes in aromatic molecules. Part 6.—The absorption spectra and acidity constants of phenoxyl radicals

Land, E. J.; Porter, G.; Strachan, E.
Royal Society of Chemistry — Jan 1, 1961
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Abstract

PRIMARY PHOTOCHEMICAL PROCESSES IN AROMATIC MOLECULES PART 6.-TuTF, ABSORPTION SPECTRA AND ACIDITY CONSTANTS OF PHENOXYL RADICALS BY E. J. LAND, G. PORTER AND E. STRACHAN Dept. of Chemistry, Sheffield University Received 28th October, 1960 Phenoxyl radicals and their derivatives have been prepared by flash photolysis in gaseous and liquid systems, by chemical oxidation and by photolysis of rigid solutions. Their spectra have been recorded and the longer wavelength system, expected on theoret- ical grounds, has been observed. Investigations of the spectrum as a function of pH show that these radicals are very weak bases and that, contrary to the interpretations of some other workers, the spectra observed under all conditions except those of very high acidity are to be attributed to neutral unprotonated radicals. The photolysis of aromatic hydrocarbons having alkyl, amino or hydroxyl groups, gives rise to transient products which have been attributed to the benzyl, anilino and phenoxyl radicals respectively and to their derivatives. These absorp- tion spectra were first observed by Porter and Wright 1 in flash photolysis studies of aromatic vapours and were detected shortly afterwards by Norman and Porter 2 as trapped products of photolysis in glassy solutions at low temperatures. Whilst the benzyl

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Transactions of the Faraday Society – Royal Society of Chemistry

Published: Jan 1, 1961

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