Carbon allotropes built from rings of two-coordinate atoms, known as cyclo[n]carbons, have fascinated chemists for many years, but until now they could not be isolated or structurally characterized, due to their high reactivity. We generated cyclo[18]carbon (C18) using atom manipulation on bilayer NaCl on Cu (111) at 5 Kelvin by eliminating carbon monoxide from a cyclocarbon oxide molecule C24O6. Characterization of cyclo[18]carbon by high-resolution atomic force microscopy revealed a polyynic structure with defined positions of alternating triple and single bonds. The high reactivity of cyclocarbon and cyclocarbon oxides allows covalent coupling between molecules to be induced by atom manipulation, opening an avenue for the synthesis of other carbon allotropes and carbon-rich materials from the coalescence of cyclocarbon molecules.

Cyclo[18]carbon (C 18 , a molecular carbon allotrope) can be synthesized by dehalogenation of a bromocyclocarbon precursor, C 18 Br 6 , in 64% yield, by atomic manipulation on a sodium chloride bilayer on Cu(111) at 5 K, and imaged by high-resolution atomic force microscopy. This method of generating C 18 gives a higher yield than that reported previously from the cyclocarbon oxide C 24 O 6 . The experimental images of C 18 were compared with simulated images for four theoretical model geometries, including possible bond-angle alternation: D 18 h cumulene, D 9 h polyyne, D 9 h cumulene, and C 9 h polyyne. Cumulenic structures, with ( D 9 h ) and without ( D 18 h ) bond-angle alternation, can be excluded. Polyynic structures, with ( C 9 h ) and without ( D 9 h ) bond-angle alternation, both show a good agreement with the experiment and are challenging to differentiate.

Using low-temperature scanning tunneling microscopy, we show that monolayer hexagonal boron nitride (h-BN) on Ir(111) acts as ultrathin insulating layer for organic molecules, while simultaneously templating their self-assembly. Tunneling spectroscopy experiments on cobalt phthalocyanine (CoPC) reveal narrow molecular resonances and indicate that the charge state of CoPC is periodically modulated by the h-BN moiré superstructure. Molecules in the second layer show site-selective adsorption behavior, allowing the synthesis of molecular dimers that are spatially ordered and inaccessible by usual chemical means.

On-surface synthesis with molecular precursors has emerged as the de facto route to atomically well-defined graphene nanoribbons (GNRs) with controlled zigzag and armchair edges. On Au(111) and Ag(111) surfaces, the prototypical precursor 10,10′-dibromo-9,9′-bianthryl (DBBA) polymerizes through an Ullmann reaction to form straight GNRs with armchair edges. However, on Cu(111), irrespective of the bianthryl precursor (dibromo-, dichloro-, or halogen-free bianthryl), the Ullmann route is inactive, and instead, identical chiral GNRs are formed. Using atomically resolved noncontact atomic force microscopy (nc-AFM), we studied the growth mechanism in detail. In contrast to the nonplanar BA-derived precursors, planar dibromoperylene (DBP) molecules do form armchair GNRs by Ullmann coupling on Cu(111), as they do on Au(111). These results highlight the role of the substrate, precursor shape, and molecule–molecule interactions as decisive factors in determining the reaction pathway. Our findings establish a new design paradigm for molecular precursors and opens a route to the realization of previously unattainable covalently bonded nanostructures.

Hexagonal boron nitride (h-BN) is a prominent member in the growing family of two-dimensional materials with potential applications ranging from being an atomically smooth support for other two-dimensional materials to templating growth of molecular layers. We have studied the structure of monolayer h-BN grown by chemical vapor deposition on Ir(111) by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) experiments and state-of-the-art density functional theory (DFT) calculations. The lattice mismatch between the h-BN and Ir (111) surface results in the formation of a moiré superstructure with a periodicity of ∼29Å and a corrugation of ∼0.4Å. By measuring the field emission resonances above the h-BN layer, we find a modulation of the work function within the moiré unit cell of ∼0.5 eV. DFT simulations for a 13-on-12 h-BN/Ir(111) unit cell confirm our experimental findings and allow us to relate the change in the work function to the subtle changes in the interaction between boron and nitrogen atoms and the underlying substrate atoms within the moiré unit cell. Hexagonal boron nitride on Ir(111) combines weak topographic corrugation with a strong work function modulation over the moiré unit cell. This makes h-BN/Ir(111) a potential substrate for electronically modulated thin film and heterosandwich structures.