Near edge X-ray absorption fine structure and X-ray photoelectron spectroscopy have been employed to follow the reversible trans to cis isomerization of tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). For one monolayer the molecules adopt an adsorption geometry characteristic for the trans-TBA isomer. The azo-bridge (N = N) is aligned nearly parallel to the surface and the phenyl rings exhibit a planar orientation with a small tilt angle ~4° with respect to the surface normal. Illumination of the molecular layer at 455 nm triggers the trans to cis isomerization which is associated with a pronounced change of the geometrical and electronic structure. The N1s to pi- transition of the central azo-bridge shifts by ~0.45 eV to higher photon energy and the transition dipole moment (TDM) is tilted by ~59° with respect to the surface normal. The pi--system of one phenyl ring is tilted by about 30° with respect to the surface normal, while the second ring plane is oriented nearly perpendicular to the surface. This reorientation is supported by a shift and broadening of the C-H resonances associated with the tert-butyl legs of the molecule. These findings support a configuration of the photo-switched TBA molecule on Au(111) which is comparable to the cis-isomer of the free molecule. In the photo-stationary state ~ 53 % of the TBA molecules are switched to the cis configuration. Thermal activation induces the back reaction to trans-TBA.
The original publication is available at Phys. Chem. Chem. Phys. by link DOI: 10.1039/b924409c