Roles of diffusion and activation barrier on the appearance of Marcus inversion behavior: a study of a photoinduced electron-transfer reaction in aqueous triblock copolymer (p123) micellar solutions.

Photoinduced electron transfer (ET) reactions between amines and a series of coumarins have been investigated using fluorescence-quenching measurements in aqueous P123 triblock copolymer micellar solutions. Fluorescence spectral characteristics and fluorescence anisotropy measurements indicated a nearly similar microenvironment for all of the coumarins used in P123 micelles. Substantial quenching of coumarin fluorescence in the presence of amines has been observed. The quenching rates (k(q)(TR)) are largely reduced in the P123 micelle as compared to those in other micelles (sodium dodecyl sulfate (SDS), Triton-X 100 (TX-100), cetyl trimethyl ammonium bromide (CTAB), and dodecyl trimethyl ammonium bromide (DTAB)), which is probably due to larger coumarin-amine separations in the micellar phase. The k(q)(TR) values, when plotted against free energy changes (DeltaG degrees), follow a Marcus predicted bell-shaped correlation. The estimated activation energy for the ET reactions follow an inverse bell-shaped correlation with DeltaG degrees. Present results indicate that the appearance of Marcus inversion is primarily related to the changes in the activation barrier, as predicted from the Marcus ET theory. As the k(q)(TR) values are higher than the estimated bimolecular diffusional rate constant, the role of reactant diffusion on the quenching kinetics in the P123 micelle is negligible. The appearance of Marcus inversion at unexpectedly lower exergonicity has been rationalized on the basis of slow solvent relaxation and by the application of the two-dimensional ET (2DET) theory. Critical analysis of the present results establishes that the inversion in the ET rates at high exergonicity is not due to the alteration in the diffusion parameters of the reactants, as has been suggested in some recent reports. Instead, it is evident that the inversion in quenching rates at high exergonicity is due to the alteration in the activation barrier for the ET reactions.