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• W2289687887 abstract "The photochemistry of pivaloyl, benzoyl, 4‐phenylbenzoyl, and 2‐anthroyl azides has been studied using femtosecond (fs) time‐resolved infrared (TRIR) and UV–vis spectroscopy and interpreted with the aid of computational chemistry. Density functional theory calculations revealed a significant difference in the nature of the lowest singlet excited state for these carbonyl azides. The lowest singlet excited states ( S 1 ) of p ‐phenylbenzoyl and 2‐anthroyl azides are (π,π*) in nature, while the pivaloyl and benzoyl azides S 1 states involve ( n ,π*) excitations. Nevertheless, for all acyl azides studied here, a similar, and intense, IR band at about 2100 cm −1 has been detected in the ultrafast TRIR experiments following 270 nm excitation. These bands were shifted to lower energy by about 100 cm −1 relative to the N 3 stretching mode for the ground states of these azides. These 2100 cm −1 vibrational bands were assigned to the S 1 states of acyl azides in agreement with density functional theory calculations. The decay of the acyl azide S 1 states was described by bi‐exponential functions. The fast component was attributed to the decay of the hot S 1 state and the longer component to the decay of the thermally relaxed S 1 state. A strong and broad transient absorption in the 350–650 nm spectral range was observed in the fs UV–vis experiments for p ‐phenylbenzoyl and 2‐anthroyl azides. The carrier of this absorption also decayed bi‐exponentially, and the time constants were in excellent agreement with those found in the fs TRIR experiments. The slow component of the S 1 state decay was found to be dependent on the solvent polarity. When the lifetime of the acyl azide S 1 state is substantially longer than the time constant for vibrational cooling of nascent (hot) isocyanate, the correlation between the S 1 decay and isocyanate formation was clear. The 270 nm excitation populates the S n ( n ≥ 2) states of these acyl azides. It was established that a hot nitrene is produced more efficiently from both the S n and hot S 1 states than from the relaxed S 1 state of these acyl azides. Thus, time‐resolved study provides direct experimental evidence that the S 1 state is the precursor of nitrene only when the S 1 state is pumped directly and when the S 1 state lifetime is longer than the time constant of vibrational cooling of the newborn nitrene. All of these results are consistent with the data obtained recently for 2‐napththoyl azide. Copyright © 2012 John Wiley & Sons, Ltd." @default.
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• W2289687887 date "2012-01-17" @default.
• W2289687887 modified "2023-09-26" @default.
• W2289687887 title "An ultrafast time-resolved infrared and UV-vis spectroscopic and computational study of the photochemistry of acyl azides" @default.
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• W2289687887 doi "https://doi.org/10.1002/poc.2903" @default.
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