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 theoretical 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 absorption spectra of the anilino radical, the protonated radical cation and the spectra of a number of anilino derivatives have been recorded in various solvents by flash photolysis of the corresponding anilines. Acidity constants, extinction coefficients and rate constants of the secondorder decay of the radicals have been determined.The spectra of the isoelectronic series 0CH2,ONH and 00 and their derivatives have now been fairly completely characterized and a comparison is made of their wavelengths and extinction coefficients.
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