Photoinduced reversible changes in the electronic structure of photochromic diarylethene films

The change in the valence electronic structure upon switching of two photochromic diarylethene derivatives, i.e. 1,2-bis(2-methyl-5-p-tolylthiophen-3-yl)cyclopent-1-ene (DAE1) and 1,2-bis(5-(4-hexyloxycarbonylphenyl)-2-methylthiophen-3-yl)cyclopent-1-ene (DAE2), was measured by photoelectron spectroscopy. Switching between open and closed forms was followed in situ upon illumination. The increase of the ionization energy from the closed to the open form was 0.85 eV for DAE1 and 0.80 eV for DAE2. For DAE1, the work function also decreased by 0.25 eV upon switching, which is explained by a decrease of the intrinsic molecular dipole moment and a preferential orientation of molecules in thin films.