In recent years, solid-state photochemistry has proven to have high synthetic potential; namely, chemo- and stereo-selectivities, facile scale up, quantitative yields, and solvent free conditions. Yet, one of the current disadvantages of solid-state photochemistry is elucidating mechanisms and associated kinetics. To meet these current challenges in solid-state photochemistry, our group, has used nanocrystals suspended in water to overcome the complications in transmission spectroscopy in the solid-state. We chose 2-azidobiphenyls as a model system to expand the scope and feasibility of performing transmission spectroscopy using nanocrystalline suspensions.<br/>Previously, Platz and co-workers have thoroughly investigated the reaction pathway of 2-azidobiphenyl in solution using laser flash photolysis. 2-azidobiphenyl can undergo photo-induced denitrogenation to generate the singlet nitrene. The singlet nitrene has various pathways it can undergo. Under solid-state conditions, the singlet nitrene can insert into the neighboring aromatic ring to provide the isocarbazole species. The isocarbazole rapidly undergoes a 1,5-H shift to provide the carbazole product. Given the photochemical reaction pathway of 2-azidobiphenyl in solution as well as product analysis of 2-azidobiphenyl in the solid-state by Sugawara, we set out to explore various transient kinetics in solution as well as in solid-state by implementing nanocrystalline suspensions in water.<br/>We synthesized various derivatives of 2-azidobiphenyl and analyzed their kinetics traces in both pentane and in nanocrystalline suspensions.

Photochemistry of crystalline 2-azidobiphenyls to form crystalline carbazoles: Scope, laser flash photolysis and solid-to-solid studies

253rd National Meeting (2017)

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