Intermolecular electron-transfer mechanisms via quantitative structures and ion-pair equilibrium for self-exchange of anionic (dinitrobenzenide) donors

The quantitative basis for evaluating the complex equilibrium and intrinsic (self-exchange) electron transfer rates for the potassium salts of p-dinitrobenzene radical anion [DNB(super -)] are provided by definitive X-ray structures of 'separated' versus 'contact' ion pairs. Three types of ion pairs, K(L)(super +)DNB(super -), are classified as Classes S, M and C namely, the specific ligation of K(super +) with different macrocylic polyether ligands (L).