Molecular species in fluid solution, in rigid matrices, and attached to surfaces are to be considered with the overall objectives and significance being the correlation of electronic structure and reactivity and in establishing the detailed pathway by which light- and electrochemically-induced reactions occur. There are potential applications in electronic switching devices, microelectronics, semiconductors and related electronic materials. Photochemical and electrochemical studies of organometallic molecules in fluid solution, in rigid media, and on surfaces are proposed. The objective of the research is to understand chemical and physical consequences associated with changes in the electron configuration of the metal complex. Additionally, chemical and spectroscopic characterization of photochemically and electrochemically generated intermediates will be carried out in order to better understand mechanisms of photoreactions and redox processes. Specific systems to be investigated include metal-metal bonded complexes to determine factors influencing photosubstitution reactivity and the reactivity of coordinatively unsaturated metal-metal bonded systems. Another class of molecules to be investigated are mononuclear systems to establish aspects of the mechanism of stoichiometric and catalytic reactions. The approach involves using light to generate coordinatively unsaturated species at low temperature followed by warm up experiments to effect thermal reactions. The remaining thrust of the research involves synthesis of redox polymers to illustrate that reactivity of bound organometallic subunits can be tuned by electrochemical means.
