Photochemistry of 2-naphthoyl azide. An ultrafast time-resolved UV-Vis and IR spectroscopic and computational study

Jacek Kubicki, Yunlong Zhang, Shubham Vyas, Gotard Burdzinski, Hoi Ling Luk, Jin Wang, Jiadan Xue, Huo Lei Peng, Elena A. Pritchina, Michel Sliwa, Guy Buntinx, Nina P. Gritsan, Christopher M. Hadad, Matthew S. Platz

Research output: Contribution to journalArticle

41 Scopus citations

Abstract

The photochemistry of 2-naphthoyl azide was studied in various solvents by femtosecond time-resolved transient absorption spectroscopy with IR and UV-vis detection. The experimental findings were interpreted with the aid of computational studies. Using polar and nonpolar solvents, the formation and decay of the first singlet excited state (S1) was observed by both time-resolved techniques. Three processes are involved in the decay of the S1 excited state of 2-naphthoyl azide: intersystem crossing, singlet nitrene formation, and isocyanate formation. The lifetime of the S1 state decreases significantly as the solvent polarity increases. In all solvents studied, isocyanate formation correlates with the decay of the azide S 1 state. Nitrene formation correlates with the decay of the relaxed S1 state only upon 350 nm excitation (S0 → S 1 excitation). When Sn (n ≥ 2) states are populated upon excitation (λex = 270 nm), most nitrene formation takes place within a few picoseconds through the hot S1 and higher singlet excited states (Sn) of 2-naphthoyl azide. The data correlate with the results of electron density difference calculations that predict nitrene formation from the higher-energy singlet excited states, in addition to the S1 state. For all of these experiments, no recovery of the ground state was observed up to 3 ns after photolysis, which indicates that both internal conversion and fluorescence have very low efficiencies.

Original languageEnglish (US)
Pages (from-to)9751-9761
Number of pages11
JournalJournal of the American Chemical Society
Volume133
Issue number25
DOIs
StatePublished - Jun 29 2011

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Kubicki, J., Zhang, Y., Vyas, S., Burdzinski, G., Luk, H. L., Wang, J., Xue, J., Peng, H. L., Pritchina, E. A., Sliwa, M., Buntinx, G., Gritsan, N. P., Hadad, C. M., & Platz, M. S. (2011). Photochemistry of 2-naphthoyl azide. An ultrafast time-resolved UV-Vis and IR spectroscopic and computational study. Journal of the American Chemical Society, 133(25), 9751-9761. https://doi.org/10.1021/ja109098w