Graphene nanoribbons (GNRs) are excellent candidates for next-generation electronic materials. Unlike GNRs produced by "top-down" methods such as lithographical patterning of graphene and unzipping of carbon nanotubes that cannot reach structural perfection, the fabrication of structurally well-defined GNRs has been achieved by a "bottom-up" organic synthesis via solution-mediated or surface-assisted cyclodehydrogenation. Specifically, non-planar polyphenylene precursors were first "build up" from small molecules, and then "graphitized" and "planarized" to yield GNRs. However, fabrication of processable and longitudinally well-extended GNRs has remained a major challenge. Here we report a "bottom-up" solution synthesis of long (>200 nm), liquid-phase processable GNRs with well-defined structure and a large optical bandgap of 1.88 eV. Scanning probe microscopy demonstrates self-assembled monolayers of GNRs, and non-contact, time-resolved Terahertz conductivity measurements reveal excellent charge-carrier mobility within individual GNRs. Such structurally well-defined GNRs offer great opportunities for fundamental studies into graphene nanostructures, as well as development of GNR-based nanoelectronics.DOI: 10.1038/NCHEM.1819 http://www.nature.com/nchem/journal/v6/n2/abs/nchem.1819.html 2 Graphene nanoribbons (GNRs), defined as nanometre-wide strips of graphene, are attracting increasing attention as highly promising candidates for next generation semiconductor materials 1,2,3,4 . Quantum confinement effects impart GNRs with semiconducting properties, i.e. with a finite bandgap, which critically depends on the ribbon width and its edge structure 1,3 . Fabrication of GNRs has been primarily carried out by "top-down" approaches such as lithographical patterning of graphene 5,6 and unzipping of carbon nanotubes 7,8 , revealing their semiconducting nature and excellent transport properties 1 . However, these methods are generally limited by low yields and lack of structural precision, leading to GNRs with uncontrolled edge structures.In contrast, a "bottom-up" chemical synthetic approach based on solution-mediated 9,10,11,12,13 or surface-assisted 14 cyclodehydrogenation, namely "graphitization" and "planarization", of tailor-made three-dimensional polyphenylene precursors offers an appealing strategy for making structurally well-defined and homogeneous GNRs. The polyphenylene precursors are built up from small molecules, and thus their structures can be tailored within the capabilities of modern synthetic chemistry 15 . However, GNRs (>30 nm) produced by solution-mediated methods have been precluded from unambiguous structural characterization, i.e. microscopic visualization, due to their limited processability 9,12 . On the other hand, GNRs produced by the surface-assisted protocol have been characterized to be atomically precise using scanning tunnelling microscopy (STM) 14 . Nevertheless, this method can only provide a limited amount of GNR material, which is further bound to a metal surface, impeding wide...

Oxidative cyclodehydrogenation of laterally extended polyphenylene precursor allowed bottom-up synthesis of structurally defined graphene nanoribbons (GNRs) with unprecedented width. The efficiency of the cyclodehydrogenation was validated by means of MALDI-TOF MS, FT-IR, Raman, and UV-vis absorption spectroscopies as well as investigation of a representative model system. The produced GNRs demonstrated broad absorption extended to near-infrared region with the optical band gap of as low as 1.12 eV.

STM brings to light chirality aspects of the self-assembly of a functionalized helicene at the interface between a liquid and the solid substrates, gold and graphite. This reveals conditions for conglomerate formation.

The self-assembly of multicomponent networks at the liquid-solid interface between Au(111) or highly oriented pyrolytic graphite (HOPG) and organic solvents was investigated using scanning tunneling microscopy. Alkoxylated dehydrobenzo[12]annulene (DBA) derivatives form hexagonal nanoporous networks, which trap either single molecules of coronene (COR) or small clusters of COR and isophthalic acid to form multicomponent networks. The pattern of interdigitation between alkyl chains from DBA molecules produces hexagonal pores that are either chiral or achiral. On Au(111) substrates multicomponent networks display an ordered superlattice arrangement of chiral and achiral pores. In comparison, similar networks on HOPG display only chiral pores. The unique superlattice structure observed on Au(111) is related to a lower energetic preference for chiral pores than on HOPG and increased diffusion barriers for guest molecules. The increased diffusion barriers for guests allow them to act as nucleation sites for the formation of achiral pores. Following the initial nucleation of an achiral pore, restrictions imposed by the accommodation of guests within the porous network mean that subsequent growth naturally leads to the formation of the superlattice structure.

Supramolecular self-assembly of suitably functionalized building blocks on surfaces can serve as an excellent test-bed to gain understanding and control over multicomponent self-assembly in more complex matter. Here we employ a powerful combination of scanning tunnelling microscopy (STM) and molecular modeling to uncover two-dimensional (2D) crystallization and mixing behavior of a series of alkylated building blocks based on dehydrobenzo[12]annulene, forming arrays of nanowells. Thorough STM investigation employing high-resolution spatial imaging, use of specially designed marker molecules, statistical analysis and thermal stability measurements revealed rich and complex supramolecular chemistry, highlighting the impact of odd-even effects on the phase behavior. The methodology and analysis presented in this work can be easily adapted to the self-assembly of other alkylated building blocks.