Photoisomerization of Protonated Azobenzenes in the Gas Phase

Because of their high photoisomerization efficiencies, azobenzenes and their functionalized derivatives are used in a broad range of molecular photoswitches. Here, the photochemical properties of the trans isomers of protonated azobenzene (ABH⁺) and protonated 4-aminoazobenzene (NH₂ABH⁺) cations are investigated in the gas phase using a tandem ion mobility spectrometer. Both cations display a strong photoisomerization response across their S₁ ← S₀ bands, with peaks in their photoisomerization yields at 435 and 525 nm, respectively, red-shifted with respect to the electronic absorption bands of the unprotonated AB and NH₂AB molecules. The experimental results are interpreted with the aid of supporting electronic structure calculations considering the relative stabilities and geometries of the possible isomers and protomers and vertical electronic excitation energies.