PULSE-RADIOLYSIS AND FLASH-PHOTOLYSIS STUDIES OF ARYLALKYLAMINES IN AQUEOUS-SOLUTIONS - PRIMARY PHOTOPROCESSES

The photophysical processes leading to photoionization and photodissoc iation in the arylalkylamines benzylamine and benzhydrylamine were exa mined as a function of pH in aqueous solution using a KrF excimer lase r. The main photolytic reaction observed for the amines is photoioniza tion. The hydrated electron subsequently reacts with the amine leading to deamination when the amino group is in the protonated form, wherea s, at pH approximate to 11.0, e(aq)(-) adds to the benzene ring, Photo dissociation processes occurring via C-H and C-C bond rupture are also observed and various transient intermediates can be identified by gen eration in appropriate pulse radiolysis experiments under suitable con ditions. The two-step photoionization occurs via the triplet excited s tate as indicated by the heavy atom effect. In contrast, photodissocia tion occurs via a monophotonic process. (C) 1997 Elsevier Science S.A.