Reactive intermediates formed by the consecutive photolyses of naphthalenetetracarboxylic dianhydrides: direct observation of reactive intermediates generated by laser-induced reaction in low-temperature argon matrices

摘要

Photolyses of 1,2:5,6- and 2,3:6,7-naphthalenetetracarboxylic dianhydrides (1 and 2), which would be precursors of 1,5- and 2,6-naphthdiynes, respectively, were studied by matrix isolation and wavelength-selective irradiation techniques in order to directly observe intermediates produced stepwise. The photolyzed products in the matrices were characterized by FT-IR and UV-Vis spectroscopies with the aid of density functional theory calculations. As a result of decarboxylation and decarbonylation of dianhydride precursors, the generation of naphthyne intermediates was confirmed in both the cases of 1 and 2. The photolyses of these naphthyne intermediates resulted inthe formation of acetylenic compounds as in the case of benzdiynes. In the photolysis of 1, the final compound was assigned to deca-5-ene-1,3,7,9-tetrayne, although it was unidentified in the case of 2,