Biradical-like Reactive Intermediates

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With the support of the Organic Dynamics Program in the Chemistry Division, Professor Josef Michl, of the Department of Chemistry at the University of Colorado- Boulder, will work on three projects in the area of his traditional interest, photophysics and photochemistry. One of the projects is a continuation of a current effort to understand heavy atom effects, while two are new. In one of the latter, it is proposed to take a fresh angle of attack on the venerable problem of the molecular structure responsible for anomalous ("TICT") emission from donor-acceptor compounds, and test the proposal that a twisted biradicaloid excited state is responsible. In the other, it is proposed to separate and evaluate the electronic spectral properties of individual conformers of saturated linear chains in a complex conformer mixture. In addition, a fourth project is proposed in a research subject that is relatively new to this research group. This is a broad effort in the areas opened by the recent synthesis of carborane anions and radicals of the type CB11(CH3)12-, CB11(CH3)12., CB11(CF3)12-, etc., in the PI's laboratory, and the proposed synthesis of the still unknown CB11(CF3)12.. In the previous grant period, these compounds were shown to offer new avenues of access to inorganic and organometallic reactive intermediates, and their lithium salts catalyze several kinds of organic reactions. It is now proposed to explore the applicability of these new tools in wide areas of organic and inorganic chemistry. These fundamental studies of the synthesis and properties of reactive intermediates may have applications in lithium batteries, fuel cell membranes, and catalysts for olefin polymerization.