This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is in the area of organometallic photochemistry. The results are expected to answer important questions concerning the mechanisms of light-induced reactions of organometallic compounds and may also provide useful methodology for the synthesis of thin films of organometallic compounds. The focus of the project is photochemical and thermal arene replacement reactions of transition metal complexes. New laser dye complexes of CpRu(+) and Cp(*)Ru(+) will be synthesized,and the emission and photochemical properties of these new chromophores will be investigated. Mechanistic studies of arene release from CpRe(arene), from CpMn(biphenyl) and from bis(arene)Re(+) will focus on the importance of hapticity changes in the photochemical and thermal reactions of metal-arene and related compounds. The differences between photochemical and thermal arene displacement will be investigated by kinetic studies and through spectroscopic identification of reaction intermediates. Reaction intermediates will be characterized using rapid scan diode array and FT-IR spectrometers. Flash photolysis studies will be initiated to measure the kinetics of metal-arene dynamics by transient absorption and emission lifetime measurements. The mechanism of epoxide polymerization by CpFe(arene)+ complexes to produce thin films will be studied, and this reaction will be extended to produce chiral polymers by using chiral iron complexes as the photochemically active species.
