Roto-Cyclization of 4-Bromopicene in On-Surface Synthesis.

Progress toward single-molecule electronics relies on a thorough understanding of the understanding of local physio-chemical processes and development of synthetic routines for controlled heterocoupling. We demonstrate a structurally unexpected ring closure process for a homo-coupled 4,4'-bipicenyl, realized in on-surface synthesis. An initial covalent C-C coupling of 4-bromopicene locks at lower temperatures the position and geometrically shields part of 4,4'-bipicenyl. Employing this effect of shielding might offer a path toward controlled stepwise hetero-coupling. At higher temperatures, a thermally activated three-dimensional rotation upon hydrogen dissociation, a dehydrogenative roto-cyclization, lifts the surface dimensionality restriction, and leads to the formation of a perylene. Thereby, the shielded molecular part becomes accessible again.

Optomechanical switching of adsorption configurations of polar organic molecules by UV radiation pressure.

Using photoemission spectroscopy (PES), we have systematically investigated the behavior of polar organic molecule, chloroaluminum phthalocyanine (ClAlPc), adsorbed in the Cl-down configuration on the Ag(111) substrate at low temperature - 195 °C under UV irradiation with a range of different photon fluxes. Judging from the evolution of photoemission spectral line shapes of molecular energy states, we discovered that the Cl atoms are so robustly anchored at Ag(111) that the impinging photons cannot flip the ClAlPc molecules, but instead they crouch them down due to radiation pressure; we observe that the phthalocyanine (Pc) lobes bend down to interact with Ag atoms on the substrate and induce charge transfer from them. As photon flux is increased, radiation pressure on the Pc plane initiates tunneling of the Cl atom through the molecular plane to turn the adsorption configuration of ClAlPc from Cl-down to an upheld Cl-up configuration, elucidating an optomechanical way of manipulating the dipole direction of polar molecules. Finally, work function measurements provide a distinct signature of the resulting upheld Cl-up configuration as it leads to a large increase in vacuum level (VL), ~ 0.4 eV higher than that of a typical flat-on Cl-up configuration driven by thermal annealing.