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

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 CN 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.