Primitive Molecular Recognition Effects in Electron Transfer Processes: Modulation of ((Trimethylammonio)methyl)ferrocenium/ferrocene Self-Exchange Kinetics via Hydrophobic Encapsulation.
1H NMR line broadening measurements show that the electron self-exchange rate constant for ((trimethylamino)methyl)ferrocenium/ferrocene (TMAFc(2+/+)) in D(2)O as solvent is decreased by ca. 20-50 fold in the presence of excess beta-cyclodextrin. The rate effect is associated with the selective hydrophobic encapsulation of the ferrocene form of the redox couple (i.e., the ferrocenium form is not significantly encapsulated). Selective encapsulation leads to a coupling of electron transfer to host (cyclodextrin) transfer. Optical intervalence absorption measurements for a closely related mixed-valence system strongly suggest that the coupling decreases the self-exchange rate by increasing the thermal activation barrier-an inference that is corroborated by activation parameter measurements. The barrier increase ultimately can be understood in terms of a redox asymmetry effect upon the isolated electron transfer event, where the overall exchange mechanism likely entails sequential electron and host transfer.
Nielson
Roger M.
RM
Department of Chemistry, Northwestern University, Evanston, Illinois 60208.
Lyon
L. Andrew
LA
Hupp
Joseph T.
JT