Luminactive Gold Complexes: Synthesis and Photophysics

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This award in the Chemical Synthesis (SYN) program supports work by Professor Thomas Gray at Case Western Reserve University to carry out fundamental studies in organometallic gold chemistry. (Ligand)gold(I) fragments bind to carbon in place of terminal hydrogens. Gold is grafted to organic scaffolds at controlled positions. Sensitive functional groups survive, and harsh reagents are avoided. The gold atom promotes population of triplet excited states upon light-excitation. These triplet states persist for microseconds or longer. Ultrafast kinetics studies of gold(I) organometallics are revealing the absorption and decay characteristics of (phosphine)gold(I) aromatics. A number of conjugated chromophores, with gold at the edges, are being prepared. The structural and optical properties of these compounds are being measured. Absorption and emission spectra, and state-to-state dynamics, are understood with time-dependent density-functional theory calculations. The Gray group is also developing synthetic methods that form stable carbon-gold bonds. These reactions form isolable, readily characterized, and easily handled organometallics. This research has relevance to such applications as catalysis, light-emitting diode construction, and film deposition, among others. The work will also contribute to an undergraduate laboratory in organometallic synthesis and in photophysical characterization. This activity applies gold click-chemistry, a copper-mediated cycloaddition of gold(I) alkynyls with organic azides. The resulting triazolate complexes are characterized by static and time-resolved emission spectroscopy. The supported research is training undergraduate and graduate students for scientific careers in industry, government, the military, and academia.