The influence of the electronic structure of adsorbate–substrate complexes on photoisomerization ability

We use time-resolved two-photon photoemission to study two molecular photoswitches at the Au(111) surface, namely azobenzene and its derivative tetra- tert -butyl-azobenzene (TBA). Electronic states located at the substrate–adsorbate interface are found to be a sensitive probe for the photoisomerization of TBA. In contrast to TBA, azobenzene loses its switching ability at the Au(111) surface. Besides the different adsorption geometries of both molecules, we partly attribute the quenching in the case of azobenzene to a shift of the highest occupied molecular orbital (HOMO) with respect to the gold d-bands, which renders the hole transfer involved in the photoisomerization mechanism of TBA inefficient.