Nitrenes are electron deficient reactive intermediates with two unpaired electrons, thus they can exist as singlet or triplet. Singlet nitrenes are of great interest due to their applicability including lithography, cross-linking polymers, photoaffinity labeling etc. whereas, triplet nitrenes are used as building blocks of high spin assembles. Because of these numerous applications there is a general interest in nitrene. The common precursors of nitrenes are azides. Aryl azides are studied extensively using ultrafast methods, matrix studies etc. There exists very limited understanding/information on photoreactivity of polyaromatic hydrocarbon (PAH) azide systems. Our research goal is to increase the breadth of knowledge in photochemistry of azido-PAH’s by incorporating the PAH Corannulene. Corannulene (C20H10), consists of a five membered ring fused with five benzene rings. This unique PAH provides an interesting curved molecular structure for photochemical studies. The curved structure will be compared to other azido-PAH’s e.g., azido pyrene containing planar geometry to determine the effects of curvature on the reactivity of nitrenes. Preliminary studies using nano-second laser flash photolysis and theoretical calculation suggest formation of triplet vinyl nitrene as an intermediate upon photolysis of corannulene azide (Mechanism 1).

Generating vinyl nitrene from aromatic azides

251st National Meeting (2016)

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