Reversible electron-induced cis-trans isomerization mediated by intermolecular interactions

Reversible isomerization processes are rarely found when organic molecular switches are adsorbed on metal surfaces. One obstacle is the large energy difference of the isomeric forms, since usually the most planar conformer has the largest adsorption energy. In the example of an imine derivative, we show a strategy for also stabilizing the non-planar isomer by intermolecular bonding to its neighbors. Tunneling electrons from the tip of a scanning tunneling microscope can then be used to induce reversible switching between the trans?and cis-like state. Supported by model force-field calculations, we illustrate that the most probable cause of the enhanced stability of the three-dimensional cis?state at specific adsorption sites is the electrostatic interaction with N sites of the neighboring molecule.