Effect of electron-donating substitution on the triplet state reactivities of 1-nitronaphthalene

Nitro-polycyclic aromatic hydrocarbons (nitro-PAHs), often found in polluted air, are carcinogenic and muta-genic. The nitro group increases the spin-orbit coupling and results in the lowest excited triplet (T1) on the picosecond time scale with a high yield. The electron-donating substituents have a significant influence on the photophysics and photochemistry of nitro-PAHs. We used transient absorption spectroscopy and kinetic analysis to investigate the reactivities of the T1 state 1-methoxy-4-nitronaphthalene (3MeO-NN) and 1-methyl-4-nitro -naphthalene (3Me-NN). The results show that the methoxy and methyl substitutions have a minor effect on their hydrogen abstraction and electron accepting abilities. The main distinction is their reaction rates towards protons. The second order rate constant of 3MeO-NN towards protons is three orders of magnitude greater than that of 3Me-NN, indicating that 3MeO-NN has a stronger hydrogen bond accepting ability. The kinetic analysis reveals that the dimer of 2,2,2-trifluoroethanol participates in the reaction with 3MeO-NN. These results suggest that the formation of the hydrogen-bonded complex is responsible for the unusually short lifetime of 3MeO-NN in methanol solution and the lack of hydrogen abstraction radicals during the decay of 3MeO-NN in methanol.

Automated summary

Nitro-polycyclic aromatic hydrocarbons (nitro-PAHs), which are often found in polluted air, are carcinogenic and mutagenic. In this study, the reactivities of two nitro-PAHs were investigated using spectroscopy and kinetic analysis. The results showed that the substituents on the compounds have different effects on their hydrogen abstraction and electron accepting abilities, with one compound exhibiting a stronger hydrogen bond accepting ability.