Modern Chemistry & Applications

Abstract

On the Primary Reaction Pathways in the Photochemistry of Nitro-Polycyclic Aromatic Hydrocarbons

Carlos E Crespo-Hernández, Aaron Vogt R and Briana Sealey

The primary reaction pathways in the photochemistry of nitro-polycyclic aromatic hydrocarbons under specific laboratory conditions are briefly summarized. In addition, photochemical data is presented for 2-nitronaphthalene, 1-nitronaphthalene, and 2-methyl-1-nitronaphthalene in cyclohexane and acetonitrile solutions under aerobic and anaerobic conditions. It is shown that molecular oxygen significantly reduces the photodegradation quantum yield of 1-nitronaphthalene and 2-methyl-1-nitronaphthalene by 63% and 81%, respectively, whereas 2-nitronaphthalene is photoinert in both solvents under aerobic and anaerobic conditions. In addition, it is proposed that recombination of the aryl and nitrogen (IV) dioxide geminate radical pair within the solvent cage or internal conversion of an initially formed intramolecular charge transfer state may play an important role in the fraction of excited molecules that returns to the ground state in 1-nitronaphthalene and 2-methyl-1-nitronaphthalene. Scavenging of radical species by molecular oxygen and the generation of singlet oxygen in high yield are proposed to contribute to the photochemistry of these nitro-naphthalene derivatives in solution.