Tuning the Planarity of an Aromatic Thianthrene-Based Molecule on Au(111)

Nonplanar aromatic molecules are interesting systems for organic electronics and optoelectronics applications due to their high stability and electronic properties. By using scanning tunneling microscopy and spectroscopy, we investigated thianthrene-based molecules adsorbed on Au(111), which are nonplanar in the gas phase and the bulk solid state. Varying the molecular coverage leads to the formation of two different kinds of self-assembled structures: close-packed islands and quasi-one-dimensional chains. We found that the molecules are nonplanar within the close-packed islands, while the configuration is planar in the molecular chain and for single adsorbed molecules. Using vertical tip manipulation to isolate a molecule from the island, we demonstrate the conversion of a nonplanar molecule to its planar configuration. We discuss the two different geometries and their electronic properties with the support of density functional theory calculations.