Combined Effects of Hemicolligation and Ion Pairing on Reduction Potentials of Biphenyl Radical Cations

Formal reduction potentials of highly oxidizing and short-lived radical cations of substituted biphenyls generated by pulse radiolysis in 1,2-dichloroethane (DCE) were measured using a redox equilibrium ladder method. The effect of halide ion-radical interactions on reduction potentials of biphenyls was examined by utilizing the ability of DCE to release Cl- in the vicinity of the radical cation. The Hammett correlation of measured potentials across a range of over 700 mV shows saturation at high Hammett sigma values. This effect has been explained by both ion-pairing and hemicolligation interactions between biphenyl radical cations and Cl- and appears to modulate reduction potentials by as much as 400 mV. This finding offers a convenient way to manipulate the energetics of electron transfer involving organic redox species.

Automated summary

The formal reduction potentials of highly oxidizing and short-lived radical cations of substituted biphenyls generated in 1,2-dichloroethane (DCE) were measured using a redox equilibrium ladder method. The effect of halide ion-radical interactions on the reduction potentials of biphenyls was investigated, and it was found that the measured potentials saturated at high Hammett sigma values, indicating the influence of ion-pairing and hemicolligation interactions. This study provides a convenient way to manipulate the energetics of electron transfer involving organic redox species.