Substrate-controlled linking of molecular building blocks: Au(111) vs. Cu(111)

The coupling of dibromohexabenzocoronene (Br2-HBC) as a precursor molecule is investigated by scanning tunneling microscopy (STM) on two noble metal surfaces: Au(111) and Cu(111). It is found that the on-surface polymerization of molecular building blocks equipped with halogen atoms is strongly influenced by the choice of the substrate. While on Au(111) a heating step of up to 520 K is required to activate the molecules and form polymers, on Cu(111) the catalytic reactivity causes activation already below room temperature. Due to the different substrates, the intramolecular bonds in the polymers between the HBC units differ: The HBC molecules are covalently coupled on Au(111) while on Cu(111) a copper adatom mediates the bonding. This effect is proven by the comparison with gas phase calculations and by lateral manipulation with the STM tip. The choice of the substrate thus does not only define the activation temperature but also lead to different bonding strengths between the molecular building blocks.