A unified approach to the synthesis of the series of higher acenes up to previously unreported undecacene has been developed through the on‐surface dehydrogenation of partially saturated precursors. These molecules could be converted into the parent acenes by both atomic manipulation with the tip of a scanning tunneling and atomic force microscope (STM/AFM) as well as by on‐surface annealing. The structure of the generated acenes has been visualized by high‐resolution non‐contact AFM imaging and the evolution of the transport gap with the increase of the number of fused benzene rings has been determined on the basis of scanning tunneling spectroscopy (STS) measurements.

The on-surface synthesis of nonacene has been accomplished by dehydrogenation of an air-stable partially saturated precursor, which could be aromatized by using a combined scanning tunneling and atomic force microscope as well as by on-surface annealing. This transformation allowed the in-detail analysis of the electronic properties of nonacene molecules physisorbed on Au(111) by scanning tunneling spectroscopy measurements. The spatial mapping of molecular orbitals was corroborated by density functional theory calculations. Furthermore, the thermally induced dehydrogenation uncovered the isomerization of intermediate dihydrononacene species, which allowed for their in-depth structural and electronic characterization.

Nanographenes on oxides: The growth of nanographene islands and ribbons on metal surfaces can be accomplished on single-crystal metal surfaces through carbon-carbon coupling reactions, but the surfaces of oxides do not assist these reactions. Kolmer et al. show that fluorinated aryl groups can be coupled to form nanographenes on the rutile surface of titanium oxide. The fluorine substitution of the aryl groups was selected so that as the carbon-fluorine bonds were thermally activated, a stepwise process sequentially added aromatic rings around a central aryl group until it was completely substituted. Science , this issue p. 57

Surface assisted synthesis has become a powerful approach for generation of molecular nanostructures, which could not be obtained via traditional solution chemistry. Nowadays there is an intensive search for reactions that could proceed on flat surfaces in order to boost the versatility and applicability of synthesized nano-objects. Here we propose application of atomic hydrogen combined with on-surface synthesis in order to tune the reaction pathways. We demonstrate that atomic hydrogen could be widely applied: (1) as a cleaning tool, which allows to remove halogen residues from the surface after Ullmann couplings/polymerization, (2) by reaction with surface organometallics to provide stable hydrogenated spe-cies (3) as a reagent for debromination or desulfurization of adsorbed species.