Kinetic analysis of the reactions of 1-substituted pyrene cation radicals with water in acetonitrile

Abstract

Although the spectroscopic detection of electrochemically generated pyrene cation radical (PY +) is generally difficult at room temperature in acetonitrile (AN), we could successfully observe the time changes in the absorption spectra of short-lived PY + using an electron transfer stopped-flow (ETSF) method by adopting the tris(2,4-dibromophenyl)amine cation radical (TDBPA +) as a reaction initiator. The decrease of PY + was observed to be complete within 30 ms after generating PY + via the mixing of the AN solutions of PY and TDBPA +. This decay reaction of PY + can be attributed to the reaction with a trace amount of water in AN. Thus, the reactions of 1-substituted pyrene cation radicals (XPY +) with water were systematically analyzed using the ETSF method by adding a constant amount of water. Consequently, the reactions were confirmed to be second-order in the cation radicals in all the cases. Among the derivatives, the higher stability of 1-aminopyrene + was confirmed on the basis of the slow reaction rates, and the order of the reactivity toward water was clarified to be pyrene +>1-bromopyrene +>1-methylpyrene +>1-aminopyrene +. The present results of XPY + were compared with our previous results on the reactions of 9-substituted anthracene derivative cation radicals.