With this award, the Organic and Macromolecular Chemistry Program continues its support of the work of Professor Ralf Warmuth of the Department of Chemistry at Rutgers University, New Brunswick, NJ. The research will extend the PI's work in the area of reactive intermediates trapped inside molecular cages referred to as hemicarcerands. The encapsulated intermediates will be generated photochemically from precursor molecules inside a suitable hemicarcerand cage that protects the reactive intermediate from dimerization and from reaction with molecules that are too large to enter the molecular cage. The spectroscopic properties of these reactive intermediates, their intramolecular rearrangements, and their reaction with the surrounding host or small bulk phase reactants will be investigated by NMR spectroscopy, infrared spectroscopy, and ultraviolet/visible spectroscopy. This approach, which will be used to study a variety of highly strained or electron deficient reactive intermediates, will allow studies of energetic species that are normally stable only at extremely low temperatures or for fractions of a second at room temperature. The NMR spectroscopic characterization, which is only practical using this approach, will provide new insight into the electronic, magnetic, and structural properties of these intermediates.
These investigations of encapsulated reactive intermediates and strained organic molecules, which will provide fundamental new information on chemical reactivity, will have significant impact on areas ranging from pharmaceutical chemistry to materials science. The research provides an excellent way of preparing students for future careers in industry or academia. The program is committed to achieving diversity among student researchers and will strongly encourage undergraduate students to participate.