Electron Transfer Photochemistry

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With the support of the Organic Dynamics Program in the Chemistry Division, Professor Mariano, of the Chemistry Department at the University of New Mexico, will focus on the development and mechanistic understanding of new photochemical reactions that are initiated by excited state single electron transfer (SET) and take place through the intermediacy of short-lived radical ions. The approaches taken in these studies are mechanistically grounded and, consequently, the results should contribute significantly to the understanding of ion radical chemistry and the factors that govern the nature and efficiencies of SET-promoted photochemical reactions. Furthermore, the SET-promoted photochemical reactions will be developed as practical methods for the preparation of organic substances of potential importance in biomedical areas. An example of this is found in the highly concise approach proposed for preparation of the biologically important mitocene skeleton. Although the investigations concentrate on SET-photochemical processes, they are more broadly designed to address fundamentally important questions that relate to several sub-areas of modern organic chemistry. For example, knowledge gained about the factors that govern the rates of intra-chain SET in zwitterionic biradicals derived from acceptor-polydonor systems and that control the regioselectivities and efficiencies of SET-promoted reactions of these substances are highly relevant to the areas of organic electrochemistry, and potentially, the design of new conductive materials.With the support of the Organic Dynamics Program in the Chemistry Division, Professor Mariano's studies of SET-promoted photocyclization reactions of acceptor-polydonor systems will lead to the development of new and efficient methods to prepare interesting macrocyclic compounds that could serve as effective molecular recognition and ion sensing agents. Finally, the proposed studies will have a significant impact on chemical education since they will serve as a foundation for the broad and comprehensive education of doctoral students in the areas of synthetic and physical organic chemistry.