UV-induced single and double hydrogen-atom migrations in 3,6-diimino-1,4-cyclohexadiene-1,4-diamine in a low-temperature argon matrix

Abstract

Isomerization induced by ultraviolet radiation due to intramolecular hydrogen-atom migration in 3,6-diimino-1,4-cyclohexadiene-1,4-diamine (DCD) was studied by matrix-isolation Fourier transform infrared (IR) spectroscopy and density functional theory (DFT) calculation. Two isomers produced by single and double inversion of the hydrogen atom(s) around the C N bond(s) were identified using the wavelength dependence of the IR band-intensity changes. In addition, the IR bands of an intermediate produced by single hydrogen-atom transfer from the amino to the imino group ( C – NH 2 ⋯ NH C ) in the hydrogen bond were measured and identified by a comparison with the calculated spectral patterns. These observations confirm stepwise photoisomerization of DCD.