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Ultrafast spectroscopy of arylchlorodiazirines: Hammett correlations of excited state lifetimes.

Experimental and computational studies suggest that 375 nm excitation of arylchlorodiazirines furnishes their S(1) excited states with lengthened C-N bonds, a positive charge at the para and diazirine carbon atoms, and a negative charge at the nitrogen atoms. These structures rationalize the observed solvent and substituent effects on the excited state lifetimes.