Thermal and Photochemical Reactions of Transition Metal Complexes of the Nitrogen Oxides

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This award supports research by Professor Peter C. Ford at the University of California at Santa Barbara to pursue investigations of the photochemical and thermal reactions of transition metal complexes of nitric oxide (NO) and other nitrogen oxide ligands (NOx). One goal is to develop precursors that can be photochemically activated for NO delivery to biological targets. Another goal is to characterize interactions of NO and other NOx such as nitrite ion, NO2, N2O3, the nitroxyl anion NO- and HNO, with metal centers and the influence of such interactions on the reactivities of these species. Modern kinetics instrumentation will be used to elucidate the pathways by which these compounds react, either spontaneously or under photochemical stimulation. These methods include time-resolved optical and infrared spectroscopy of reactive intermediates generated by laser flash photolysis or by rapid mixing. Computational techniques will be employed to investigate the relative energies and spectra of known and unknown compounds (using density functional theory) and to simulate the kinetics behavior observed or expected for complex reaction systems. Studies will explore the reaction mechanisms for the basic chemical transformations such as the formation and breaking of metal-ligand bonds and the atom and electron transfer reactions that constitute the chemistry of these "simple" species. Although fundamental in nature, the proposed studies have potential relevance to the design of materials displaying desirable photochemical properties for biomedical applications and for the reinterpretation of the mechanism(s) by which a prospective vasodilator is formed in the hemoglobin of red blood cells. The research also serves as a platform for the education and training of members of underrepresented groups at the graduate, undergraduate and postdoctoral levels.