Azobenzene isomerization on a reactive copper surface by efficient decoupling with bulky side groups

Azobenzene derivatives, an important class of molecular switches that undergo isomerization between trans and cis states, have been studied on various coinage metal surfaces in the past. However, on reactive copper surfaces switching turned out to be difficult. Here, we show that the use of bulky 2,6-dimethylphenyl side groups enables switching on a Cu(111) surface as studied by scanning tunneling microscopy. By applying voltage pulses from the STM tip, irreversible trans → cis isomerization of individual molecules can be induced where exactly one molecule within each unit cell is isomerized. The absence of backward cis → trans switching illustrates the importance of the adsorption structure on the potential energy landscape of azobenzene. Isomerization, which is activated by inelastic scattering of single tunneling electrons, happens in a very localized fashion, thus allowing to 'write' patterns of individual cis isomers into the homogeneous molecular layer. Our study demonstrates how the bulky spacer groups direct adsorption and self-assembly into close-packed structures, which are similar to three-dimensional molecular crystals, on the surface. In addition, they modulate the electronic coupling to the underlying substrate to maintain successful switching behavior even on the most reactive coinage metal surfaces.