Synthesis and Redox Chemistry of Tetrachalcogenotetraasteranes

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Professor Glass will lead a collaborative project involving the research groups of Professor Potapov (Irkutsk, Russia) and Professor Glass (Tucson, AZ, USA) on the synthesis and redox chemistry of tetrachalcogentetraasteranes (sulfur, selenium and tellurium) is proposed. The synthesis of these "star-shaped" molecules is based on the photodimerization of 1,4-dichalcogenins. The oxidation of these materials will be studied using the electrochemical technique of cyclic voltammetry and chemical oxidants. One-electron oxidation of these compounds may provide stable radical cations with novel structures in which the charge and the odd electron are delocalized equally over all four chalcogen atoms. Spectroscopic methods, especially EPR spectroscopy, are proposed for determining the structures of these materials. Two-electron oxidation of the heteroatom asteranes will be investigated to evaluate the theory of a-aromaticity. The dications may show unusual properties if they are a-delocalized. This possibility will be evaluated by spectroscopic methods, especially NMR spectroscopy. This proposed collaborative work combines the research strengths of Professor Potapov's group in synthetic heteroatom chemistry with that of Professor Glass' group in structural and redox chemistry in a mutually beneficial project which may extend our understanding of multicenter bonding and structural factors that affect electron-transfer.With this Award, The Organic and Macromolecular Chemistry Program and the Central and Eastern Europe Program in the Office of International Science and Engineering will support the research and international collaboration of Professor Richard S. Glass of the University of Arizona.