Azobenzene is a prototypical molecular switch which can be interconverted with UV and visible light between a trans and a cis isomer in solution. While the ability to control their conformation with light is lost for many molecular photoswitches in the adsorbed state, there are some examples for successful photoisomerization in direct contact with a surface. However, there the process is often driven by a different mechanism than in solution. For instance, photoisomerization of a

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... ed azobenzene directly adsorbed on Bi(111) occurs via electronic excitations in the substrate and subsequent charge transfer. In the present study we observe two substrate-mediated trans-cis photoisomerization reactions of the same azobenzene derivative in two different environments within a multilayer thin film on Bi(111). Both processes are associated with photoisomerization and one is around two orders of magnitude more efficient than the other. Furthermore, the cis isomers perform a thermally induced reaction which may be ascribed to a back-isomerization in the electronic ground state or to a phenyl ring rotation of the cis isomer. Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI. New J. Phys. 16 (2014) 053004 C Bronner and P Tegeder New J. Phys. 16 (2014) 053004 C Bronner and P Tegeder 3 New J. Phys. 16 (2014) 053004 C Bronner and P Tegeder 4 New J. Phys. 16 (2014) 053004 C Bronner and P Tegeder 5