Ultrafast spectroscopic study of the photochemistry and photophysics of arylhalodiazirines: direct observation of carbene and zwitterion formation.
Ultrafast photolysis (lambdaex = 270, 350, or 360 nm) of bromophenyl, chlorophenyl, fluorophenyl, and fluoro-para-trifluoromethylphenyl diazirines produces transient species which absorb broadly in the UV and visible regions. Transient decay can be fit to either mono- or biexponential functions (tau1 approximately 0.3-10 ps, tau2 approximately 10-350 ps; dependent on solvent and halogen). Fluoro- and chlorophenylcarbene are formed within the time resolution of the spectrometer (300 fs, 270 nm excitation). Bromophenyl diazirine decay (270 nm excitation) correlates with the growth of bromophenylcarbene. Solvent and substituent effects on the slower decays of the transient absorptions are consistent with assigning the carriers of transient absorption in the visible region to ring-opened zwitterionic species.
Wang
Jin
J
Department of Chemistry, The Ohio State University, Columbus, OH 43210, USA.
Burdzinski
Gotard
G
Kubicki
Jacek
J
Platz
Matthew S
MS
Moss
Robert A
RA
Fu
Xiaolin
X
Piotrowiak
Piotr
P
Myahkostupov
Mykhaylo
M