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The polarographic and voltammetric behaviour of dibiphenylene-ethene (DBPE) has been studied in benzonitrile, acetonitrile, propylene carbonate, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N,N-diethylformamide, pyridine, and ethylenediamine. The two successive reversible electron transfers have been observed in all these solvents. The separation between the formal potentials of DBPE/DBPE−• and DBPE−•/DBPE2− systems was found to vary with the properties of solvents and with the kind of supporting elecrtrolyte cations (tetraethylammonium and sodium perchlorates were used as electrolytes). The variation of redox potentials both with the solvent and the cation is discussed in terms of the donor–acceptor concept for solvent–solute interaction. Numerical analysis using both the values of the donor numbers and the acceptor numbers leads to successful description of experimental results. It has further been observed that DBPE2– dianion is protonized in ethylenediamine solutions.

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