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Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
An Ultrafast Infrared and UV-Vis Study of the Photochemistry of 2-Naphthaloxycarbonyl Azide
Jacek Kubicki1, Jiadan Xue2, Hoi Ling Luk2
1Faculty of Physics and Astronomy, Adam Mickiewicz University, Poznań, Uniwersytetu Poznańskiego 2, 61-614 Poznań, Poland.
Abstract:
The photochemistry and photophysics of 2-naphthaloxycarbonyl azide was studied in solution at ambient temperature with femtosecond (fs) time-resolved infrared (IR) and UV-vis spectroscopic methods. An upper singlet excited state of the azide, Sn (n > 1), decays by three processes: relaxation to azide S1, nitrogen extrusion and formation of the singlet nitrene, and fragmentation to form the ·OCN3 and 2-NpO· radicals. The decay of the S1 state of the azide correlates with 3-isocyanatonaphthalen-2(3H)-one formation, which, in turn, slowly converts to 3-isocyanatonaphthalen-2-ol. The singlet nitrene decays by intersystem crossing (ISC) to produce the corresponding triplet nitrene with a time constant of ∼100 ps. The results are consistent with prior electron spin resonance and ultrafast time-resolved experiments positing that the lowest-energy singlet state of aryloxycarbonylnitrenes is closed-shell and that the singlet state undergoes rapid ISC via spin-orbit coupling to the triplet ground state.
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