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To enhance the versatility of organic azides in organic synthesis, a better understanding of their photochemistry is required. Herein, the photoreactivity of azidoisoxazole 1 was characterized in cryogenic matrices with IR and UV-Vis absorption spectroscopy. The irradiation (λ = 254 nm) of azidoisoxazole 1 in an argon matrix at 13 K and in glassy 2-methyltetrahydrofuran (mTHF) at 77 K yielded nitrosoalkene 3. Density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations were used to aid the characterization of nitrosoalkene 3 and to support the proposed mechanism for its formation. It is likely that nitrosoalkene 3 is formed from the singlet excited state of azidoisoxazole 1 via a concerted mechanism or from cleavage of an intermediate singlet nitrene that does not undergo efficient intersystem crossing to its triplet configuration.more » « less
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This chapter serves as a review of the literature concerning the use of laser flash photolysis (LFP) in research reported between the years 2015 and 2018. The first half of the chapter primarily focuses on fundamental studies to characterize reactive intermediates and elucidate their reaction mechanisms, with special attention to a new LFP technique that allows transient absorption to be obtained in crystals. The detection and identification of excited states and their reactivity is also addressed. The second half of the chapter focuses on the use of LFP to understand and influence the development of photochemistry applications such as synthesis, photocages, polymerization, and photocatalysis. Finally, we briefly mention research that uses LFP but is outside the main focus of this chapter, such as the analysis of biological systems and environmental studies.more » « less
