Reversible Photoisomerization among Triplet Amino Naphthylnitrene, Triplet Diimine Biradical, and Indazole: Matrix-Isolation IR Spectra of 8‑Amino-1-naphthylnitrene, 1,8-Naphthalenediimine, and 1,2-Dihydrobenz[<i>cd</i>]indazole

Reaction mechanisms of nitrene, one of the most famous biradicals, have been frequently studied, and many spectral data have been obtained so far. In the present study, the experimental IR spectra of triplet 8-amino-1-naphthylnitrene (³ANN), a triplet diimine biradical 1,8-dihydro-1,8-naphthalenediimine (³DND), and 1,2-dihydrobenz­[<i>cd</i>]­indazole (DBI), which are produced in the UV photolysis of 1,8-diaminonaphthalene in an Ar matrix and identified by a combination method of IR spectroscopy and DFT quantum chemical calculations, are first reported. ³ANN is found to change to DBI by hydrogen-atom migration with bond making between the two nitrogen atoms upon visible-light irradiation (λ > 580 nm) with its backward reaction caused by 350 nm irradiation. In addition, ³ANN isomerizes to ³DND by 700 nm irradiation, while its backward reaction occurs upon 500 nm irradiation. The wavelength dependences of these photoisomerizations are explained in terms of their electronic transition energies estimated by time-dependent DFT calculations. It is concluded that the novel reversible photoisomerization system among ³ANN, ³DND, and DBI is totally different from the well-known photoisomerization between phenylnitrene and a seven-membered cyclic compound

Infrared and Electronic Spectra of Radicals Produced from 2‑Naphthol and Carbazole by UV-Induced Hydrogen-Atom Eliminations

The photoreaction mechanisms of 2-naphthol and carbazole in low-temperature argon matrices have been investigated by infrared and electronic absorption spectroscopy with aids of density-functional-theory (DFT) and time-dependent DFT (TD-DFT) calculations. When the matrix samples were irradiated upon UV light, 2-naphthoxyl and N-carbazolyl radicals were produced by the elimination of the H atom in the O–H group of 2-naphthol and in the N–H group of carbazole, respectively. The observed IR and electronic absorption spectra of the radicals were reproduced satisfactorily by the quantum chemical calculations. To understand a role of the radicals in the excited-state proton transfer (ESPT), the fluorescence and excitation spectra of 2-naphthol and carbazole were measured in aqueous solution at room temperature as well as in the low-temperature argon matrices. It was found that the intensity of the fluorescence emitted from carbazole anion in aqueous solution decreased when oxygen gas was blown into the solution