The photochemistry of electron donor–acceptor (EDA) complexes in micellar solutions. I. The stilbene–methylviologen system

Abstract

The association constants for the electron donor–acceptor (EDA) complexes formed between both cis-stilbene (cS) and trans-stilbene (tS) as donors and methylviologen (MV+2) as acceptor were determined in ethanol and micellar sodium dodecyl sulfate (SDS) solutions in the range of SDS concentration 0.05–0.1 M. The values obtained in micellar solutions were much higher than those in ethanol and were heavily dependent upon SDS concentration. This effect is due to an increase in the local concentration of the reactants in the micellar pseudophase. The tS fluorescence quenching by MV+2 was also studied in the same solvent media. In ethanol, the Stern–Volmer plot was found to be linear, with quenching constant (KSV) similar to the association constant determined by the absorption method. In micellar solutions, although upward curvature of the Stern–Volmer plots was observed, a reaction scheme based on static quenching via ground state EDA complex is proposed, which explains the experimental results. Irradiation in the absorption band of the EDA complexes formed by tS or cS and MV+2 was carried out in ethanol and SDS solutions, in the absence of oxygen. Only cis–trans isomerization of cS in SDS solution was observed, with a quantum yield value of Φcis = 0.012.