Abstract
The nucleophilic photosubstitution reactions, photocyanation and photohydrolysis, of 4-chloroanisole (ACl) and 4-fluoroanisole (AF) have been studied by time resolved spectroscopy and by measurements of transient photoconductivity in anhydrous and aqueous acetonitrile and tert-butyl alcohol solutions. The mechanism involves in its initial step the formation of a triplet state transient complex composed of an excited and a ground state aromatic molecule. This complex dissociates into radical ions only in the presence of water and this step determines the quantum yield of the product. The formation of a solvated electron is ruled out as a step in the substitution mechanism. Attack of the nucleophile on the radical cation yields a neutral radical from which the reaction product is formed in a single step. The transient species which have been observed spectroscopically are 3ACl*, 3AF*, [ACl δ−⋯δ+ ACl], ACl + , AF + , AClOH ·, AClCN ·, AFOH · and AFCN ·.
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