130 research outputs found
Giant edge state splitting at atomically precise zigzag edges
Zigzag edges of graphene nanostructures host localized electronic states that
are predicted to be spin-polarized. However, these edge states are highly
susceptible to edge roughness and interaction with a supporting substrate,
complicating the study of their intrinsic electronic and magnetic structure.
Here, we focus on atomically precise graphene nanoribbons whose two short
zigzag edges host exactly one localized electron each. Using the tip of a
scanning tunneling microscope, the graphene nanoribbons are transferred from
the metallic growth substrate onto insulating islands of NaCl in order to
decouple their electronic structure from the metal. The absence of charge
transfer and hybridization with the substrate is confirmed by scanning
tunneling spectroscopy (STS), which reveals a pair of occupied / unoccupied
edge states. Their large energy splitting of 1.9 eV is in accordance with ab
initio many-body perturbation theory calculations and reflects the dominant
role of electron-electron interactions in these localized states.Comment: 14 pages, 4 figure
Self-assembly and two-dimensional spontaneous resolution of cyano-functionalized [7]helicenes on Cu111
Birds of a feather flock together: STM and DFT studies provide the first example of spontaneous chiral resolution of a helicene on a surface. Racemic 6,13-dicyano[7]helicene forms fully segregated domains of pure enantiomers (2D conglomerate) on Cu(111). The propensity of the system to optimize intermolecular CNâ
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HC(Ar) hydrogen bonding and CNâ
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CN dipolar interactions translates into chiral recognition with preferential assembly of homochiral molecules
Coupled spin states in armchair graphene nanoribbons with asymmetric zigzag edge extensions
Carbon-based magnetic structures promise significantly longer coherence times
than traditional magnetic materials, which is of fundamental importance for
spintronic applications. An elegant way of achieving carbon-based magnetic
moments is the design of graphene nanostructures with an imbalanced occupation
of the two sublattices forming the carbon honeycomb lattice. According to
Lieb's theorem, this induces local magnetic moments that are proportional to
the sublattice imbalance. Exact positioning of sublattice imbalanced
nanostructures in graphene nanomaterials hence offers a route to control
interactions between induced local magnetic moments and to obtain graphene
nanomaterials with magnetically non-trivial ground states. Here, we show that
such sublattice imbalanced nanostructures can be incorporated along a large
band gap armchair graphene nanoribbon on the basis of asymmetric zigzag edge
extensions, which is achieved by incorporating specifically designed precursor
monomers during the bottom-up fabrication of the graphene nanoribbons. Scanning
tunneling spectroscopy of an isolated and electronically decoupled zigzag edge
extension reveals Hubbard-split states in accordance with theoretical
predictions. Investigation of pairs of such zigzag edge extensions reveals
ferromagnetic, antiferromagnetic or quenching of the magnetic interactions
depending on the relative alignment of the asymmetric edge extensions.
Moreover, a ferromagnetic spin chain is demonstrated for a periodic pattern of
zigzag edge extensions along the nanoribbon axis. This work opens a route
towards the design and fabrication of graphene nanoribbon-based spin chains
with complex magnetic ground states
On-surface synthesis of super-heptazethrene
Zethrenes are model diradicaloids with potential applications in spintronics and optoelectronics. Despite a rich chemistry in solution, on-surface synthesis of zethrenes has never been demonstrated. We report the on-surface synthesis of super-heptazethrene on Au(111). Scanning tunneling spectroscopy investigations reveal that super-heptazethrene exhibits an exceedingly low HOMOâLUMO gap of 230 meV and, in contrast to its open-shell singlet ground state in the solution phase and in the solid-state, likely adopts a closed-shell ground state on Au(111)
On-surface synthesis of polyazulene with 2,6-connectivity
Azulene, the smallest neutral nonalternant aromatic hydrocarbon, serves not only as a prototype for fundamental studies but also as a versatile building block for functional materials because of its unique opto(electronic) properties. Here, we report the on-surface synthesis and characterization of the homopolymer of azulene connected exclusively at the 2,6-positions using 2,6-diiodoazulene as the monomer precursor. As an intermediate to the formation of polyazulene, a gold-(2,6-azulenylene) chain is observed
Dramatic Acceleration of the Hopf Cyclization on Gold(111): From Enediynes to Peri-Fused Diindenochrysene Graphene Nanoribbons.
Hopf et al. reported the high-temperature 6Ï-electrocyclization of cis-hexa-1,3-diene-5-yne to benzene in 1969. Subsequent studies using this cyclization have been limited by its very high reaction barrier. Here, we show that the reaction barrier for two model systems, (E)-1,3,4,6-tetraphenyl-3-hexene-1,5-diyne (1a) and (E)-3,4-bis(4-iodophenyl)-1,6-diphenyl-3-hexene-1,5-diyne (1b), is decreased by nearly half on a Au(111) surface. We have used scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc-AFM) to monitor the Hopf cyclization of enediynes 1a,b on Au(111). Enediyne 1a undergoes two sequential, quantitative Hopf cyclizations, first to naphthalene derivative 2, and finally to chrysene 3. Density functional theory (DFT) calculations reveal that a gold atom from the Au(111) surface is involved in all steps of this reaction and that it is crucial to lowering the reaction barrier. Our findings have important implications for the synthesis of novel graphene nanoribbons. Ullmann-like coupling of enediyne 1b at 20 °C on Au(111), followed by a series of Hopf cyclizations and aromatization reactions at higher temperatures, produces nanoribbons 12 and 13. These results show for the first time that graphene nanoribbons can be synthesized on a Au(111) surface using the Hopf cyclization mechanism
OnâSurface Interchain Coupling and Skeletal Rearrangement of Indenofluorene Polymers
On-surface synthesis serves as a powerful approach to construct Ï-conjugated carbon nanostructures that are not accessible by conventional wet chemistry. Nevertheless, this method has been limited by the types and numbers of available on-surface transformations. While the majority of successful cases exploit thermally triggered dehalogenative carbonâcarbon coupling and cyclodehydrogenation, rearrangement of appropriate functional moieties has received limited research attention. Here, the unprecedented interchain coupling and thermally induced skeleton rearrangement are described of (dihydro)indeno[2,1-b]fluorene (IF) polymers on an Au(111) surface under ultrahigh vacuum conditions, leading to different ladder polymers as well as fully fused graphene nanoribbon segments containing pentagonal and heptagonal rings. Au-coordinated nanoribbons are also observed. All structures are unambiguously characterized by high-resolution scanning probe microscopy. The current results provide an avenue to fabricating a wider variety of Ï-conjugated polymers and carbon nanostructures comprising nonhexagonal rings as well as rarely explored organometallic nanoribbons.journal articl
On-surface Synthesis of Edge-Extended Zigzag Graphene Nanoribbons.
Graphene nanoribbons (GNRs) have gained significant attention in nanoelectronics due to their potential for precise tuning of electronic properties through variations in edge structure and ribbon width. However, the synthesis of GNRs with highly sought-after zigzag edges (ZGNRs), critical for spintronics and quantum information technologies, remains challenging. In this study, we present a design motif for synthesizing a novel class of GNRs termed edge-extended ZGNRs. This motif enables the controlled incorporation of edge extensions along the zigzag edges at regular intervals. We successfully demonstrate the synthesis of a specific GNR instance-a 3-zigzag-rows-wide ZGNR-with bisanthene units fused to the zigzag edges on alternating sides of the ribbon axis. The resulting edge-extended 3-ZGNR is comprehensively characterized for its chemical structure and electronic properties using scanning probe techniques, complemented by density functional theory calculations. The design motif showcased here opens up new possibilities for synthesizing a diverse range of edge-extended ZGNRs, expanding the structural landscape of GNRs and facilitating the exploration of their structure-dependent electronic properties. This article is protected by copyright. All rights reserved
Collective AllâCarbon Magnetism in Triangulene Dimers
Triangular zigzag nanographenes, such as triangulene and its Ïâextended homologues, have received widespread attention as organic nanomagnets for molecular spintronics, and may serve as building blocks for highâspin networks with longârange magnetic order, which are of immense fundamental and technological relevance. As a first step towards these lines, we present the onâsurface synthesis and a proofâofâprinciple experimental study of magnetism in covalently bonded triangulene dimers. Onâsurface reactions of rationally designed precursor molecules on Au(111) lead to the selective formation of triangulene dimers in which the triangulene units are either directly connected through their minority sublattice atoms, or are separated via a 1,4âphenylene spacer. The chemical structures of the dimers have been characterized by bondâresolved scanning tunneling microscopy. Scanning tunneling spectroscopy and inelastic electron tunneling spectroscopy measurements reveal collective singletâtriplet spin excitations in the dimers, demonstrating efficient intertriangulene magnetic coupling.This work was supported by the Swiss National Science Foundation (grant numbers 200020-182015 and IZLCZ2-170184), the NCCR MARVEL funded by the Swiss National Science Foundation (grant number 51NF40-182892), the European Unionâs Horizon 2020 research and innovation program (grant number 785219, Graphene Flagship Core 2), the Office of Naval Research (grant number N00014-18-1-2708), an ERC Consolidator grant (T2DCP, grant number 819698), the German Research Foundation (DFG) within the Cluster of Excellence Center for Advancing Electronics Dresden (cfaed) and EnhanceNano (grant number 391979941), the European Social Fund and the Federal State of Saxony (ESF-Project GRAPHD, TU Dresden), the Generalitat Valenciana and Fondo Social Europeo (grant number ACIF/2018/175), MINECO-Spain (grant number MAT2016-78625), and the Portuguese FCT (grant number UTAPEXPL/NTec/0046/2017)
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