Search

Precise synthesis of carbon-based nanostructures with well-defined structural and chemical properties is of significance towards organic nanomaterials, but remains challenging. Herein, we report on a synthesis of nitrogen-doped porous carbon nanoribbons through a stepwise on-surface polymerization. Scanning tunneling microscopy revealed that the selectivity in molecular conformation, intermolecular debrominative aryl-aryl coupling and inter-chain dehydrogenative cross-coupling determined the well-defined topology and chemistry of the final products. Density functional theory calculations predict that the ribbons are semiconductors, and the band gap can be tuned by the width of the ribbons. The atomically precise on-surface synthesis of carbon-based nanostructures is of relevance for electronic and optoelectronic devices, but achieving control over such architectures remains challenging. Here, the authors demonstrate the selective stepwise on-surface synthesis of nitrogen-doped porous carbon nanoribbons with well-defined topologies and structures, and predict variable band gaps dependent on ribbon width. [ABSTRACT FROM AUTHOR]

Control over on-surface reaction pathways is crucial but challenging for the precise construction of conjugated nanostructures at the atomic level. Herein we demonstrate a selective on-surface covalent coupling reaction that is templated by metal-organic coordinative bonding, and achieve a porous nitrogen-doped carbon nanoribbon structure. In contrast to the inhomogeneous polymorphic structures resulting from the debrominated aryl-aryl coupling reaction on Au(111), the incorporation of an Fe-terpyridine (tpy) coordination motif into the on-surface reaction controls the molecular conformation, guides the reaction pathway, and finally yields pure organic sexipyridine-p-phenylene nanoribbons. Emergent molecular conformers and reaction products in the reaction pathways are revealed by scanning tunneling microscopy, density functional theory calculations and X-ray photoelectron spectroscopy, demonstrating the template effect of Fe-tpy coordination on the on-surface covalent coupling. Our approach opens an avenue for the rational design and synthesis of functional conjugated nanomaterials with atomic precision. Synthesizing precise conjugated nanostructures on a surface requires fine control over the covalent reaction pathways. Here, the authors show that reversible coordinative bonds can be used to template on-surface C-C coupling reactions, guiding the formation of porous organic nanoribbons. [ABSTRACT FROM AUTHOR]