Abstract
Photoreaction of 2-nitrophenol has been investigated by low-temperature matrix-isolation IR spectroscopy and density-functional-theory (DFT) calculation. A reaction intermediate was identified as syn- trans 2-hydroxyphenyl nitrite, and the reaction product caused by dissociation of NO from the intermediate as 2-hydroxyphenoxyl radical. Both syn- trans and syn- cis 2-hydroxyphenyl nitrite isomers were produced by recombination of 2-hydroxyphenoxyl radical with NO in annealing at 27 K after the UV irradiation. The conformational change from cis to trans around the O–N axis occurred upon visible-light irradiation. The rate constants of photoreaction were determined by a least-squares fitting of the changes in the IR band intensities.
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