Substrate-Independent Growth of Atomically Precise Chiral Graphene Nanoribbons

Contributing to the need of new graphene nanoribbon (GNR) structures that can be synthesized with atomic precision, we have designed a reactant that renders chiral (3,1) - GNRs after a multi-step reaction including Ullmann coupling and cyclodehydrogenation. The nanoribbon synthesis has been successfully proved on different coinage metals, and the formation process, together with the fingerprints associated to each reaction step, has been studied combining scanning tunnelling microscopy, core-level spectroscopy and density functional calculations. In addition to the GNR chiral edge structure, the substantial GNR lengths achieved and the low processing temperature required to complete the reaction grant this reactant extremely interesting properties for potential applications.

Band Depopulation of Graphene Nanoribbons Induced by Chemical Gating with Amino Groups

The electronic properties of graphene nanoribbons (GNRs) can be precisely tuned by chemical doping. Here we demonstrate that amino (NH$_2$) functional groups attached at the edges of chiral GNRs (chGNRs) can efficiently gate the chGNRs and lead to the valence band (VB) depopulation on a metallic surface. The NH$_2$-doped chGNRs are grown by on-surface synthesis on Au(111) using functionalized bianthracene precursors. Scanning tunneling spectroscopy resolves that the NH$_2$ groups significantly up-shift the bands of chGNRs, causing the Fermi level crossing of the VB onset of chGNRs. Through density functional theory simulations we confirm that the hole-doping behavior is due to an upward shift of the bands induced by the edge NH$_2$ groups.

Critical role of phenyl substitution and catalytic substrate on the surface-assisted polymerization of dibromobianthracene derivatives

Understanding the nature and hierarchy of on surface reactions is a major chal- lenge for designing coordination and covalent nanostructures by means of multistep synthetic routes. In particular, intermediates and final products are hard to predict since reaction paths and their activation windows depend on the choice of both the molecular precursor design and the substrate. Here we report a systematic study of the effect of the catalytic metal surface to reveal how a single precursor can give rise to very distinct polymers that range from coordination and covalent non planar polymer chains of distinct chirality, to atomically precise graphene nanoribbons and nanoporous graphene. Our precursor consists on adding two phenyl substituents to 10,10-dibromo 9,9-bianthracene, a well-studied precursor in the on-surface synthesis of graphene nanoribbons. The critical role of the monomer design on the reaction paths is inferred from the fact that the phenyl substitution leads to very distinct products in each one of the studied metallic substrates.

Bottom up synthesis of multifunctional nanoporous graphene

Nanosize pores can turn semimetallic graphene into a semiconductor and from being impermeable into the most efficient molecular sieve membrane. However, scaling the pores down to the nanometer, while fulfilling the tight structural constraints imposed by applications, represents an enormous challenge for present top-down strategies. Here we report a bottom-up method to synthesize nanoporous graphene comprising an ordered array of pores separated by ribbons, which can be tuned down to the one nanometer range. The size, density, morphology and chemical composition of the pores are defined with atomic precision by the design of the molecular precursors. Our measurements further reveal a highly anisotropic electronic structure, where orthogonal one-dimensional electronic bands with an energy gap of ~1 eV coexist with confined pore states, making the nanoporous graphene a highly versatile semiconductor for simultaneous sieving and electrical sensing of molecular species.

On-surface route for producing planar nanographenes with azulene moieties

Large aromatic carbon nanostructures are cornerstone materials due to their increasingly active role in functional devices, but their synthesis in solution encounters size and shape limitations. New on-surface strategies facilitate the synthesis of large and insoluble planar systems with atomic-scale precision. While dehydrogenation is usually the chemical zipping reaction building up large aromatic carbon structures, mostly benzenoid structures are being produced. Here, we report on a new cyclodehydrogenation reaction transforming a sterically stressed precursor with conjoined cove regions into planar carbon platform by incorporating azulene moieties in their interior. Submolecular resolution STM is used to characterize this exotic large polycyclic aromatic compound on Au(111) yielding unprecedented insight into a dehydrogenative intramolecular aryl-aryl coupling reaction. The resulting polycyclic aromatic carbon structure shows a [18]annulene core hosting peculiar pore states confined at the carbon cavity.