The study of electron transfer in unique organic systems

The study of electron transfer in organic systems has a wide array of applications from the investigation of conducting materials for use in molecular electronics to the study of reaction mechanisms. This work investigated the nature of electron transfer is bis(ferrocenyl)polymethines as potential candidates for molecular wires and switches. Through the technique of Mossbauer spectroscopy, it was demonstrated that these materials in the solid state were true mixed-valence species. The incorporation of a soliton-containing polymethine bridge allowed for communication between the redox active ferrocene groups at a distance greater than 20 A. While more work is needed to elucidate the mechanism of this transfer process, these observations appeared to support the claim that a true molecular wire must contain a solitonic moiety in order to preclude the attenuation of electronic communication that is observed in neutral polyenes with increasing distance.;The contribution of single electron transfer (SET) in the mechanism of nucleophilic aliphatic substitution has been debated for some time. It was demonstrated that the ground state reaction of 9-mesitylfluorene with methyl iodide proceeded through a radical intermediate and that this intermediate was on the direct pathway to product formation. The formation of the 9-mesitylfluorenyl anion and subsequent oxidation by methyl iodide to the corresponding radical was confirmed by UV/Vis spectroscopy. While it was acknowledged that the S N2 pathway was inhibited due to steric hindrance about the nucleophile, this appeared to be the first example of methyl iodide acting as an oxidant in this fashion.