Electron-transfer reactions of aromatic radical ions with nucleophilic molecules

Abstract

Reactions of pyrene, anthracene and triphenylene radical cations with electron-rich species have been established as being electron transfer in nature. The reaction rates of these systems were controlled by collision through diffusional processes rather than by formation of an intermediate such as a charge-transfer complex.

Electron-transfer rates from the donor molecules to Py, An, Tr radical cations did not show significant decrease in the range –1.7 ⩽ΔG⩽ 0.2. The ΔG dependence of k_ET was simulated by using the quantum mechanical Marcus' energy-gap law with a relatively large coupling constant value for the electron-tunnelling interaction.