Abstract
The photochemistry of salicylaldoxime in solid argon has been investigated by FTIR spectroscopy and DFT calculations. The salicylaldoxime molecule trapped in the matrix from the vapor above the solid sample has the most stable syn1 conformation with an intramolecular hydrogen bond. Irradiation (λ > 320 nm) leads to conversion of the syn1 conformer into the syn3 one, in which the C(H)NOH and (C)OH groups are rotated around the C–C and C–O bonds, respectively, and the intramolecular hydrogen bond is broken. The photochemistry of syn3 involves three possible routes: (i) conversion of syn3 into anti2 conformer, this process requires rearrangement of the NOH group with respect to the C=N bond; (ii) photodissociation of salicylaldoxime into 2‐cyanophenol and water, which form a hydrogen‐bonded complex; and (iii) regeneration of the syn1 conformer. The third route is a very small contribution to the overall process. The study performed with [D~2~]salicylaldoxime indicates that the dehydration reaction of salicylaldoxime involves cleavage of the N–O bond and formation of OH and Ph(OH)C(H)N radicals in the first step. Then, the OH radical abstracts a hydrogen atom from the CH group to form 2‐cyanophenol and water molecules. When the sample is exposed to the full output of the mercury lamp the 2‐cyanophenol complex with water becomes the dominating product.