On-surface synthesis is a powerful route toward the fabrication of specific graphene-like nanostructures confined in two dimensions. This strategy has been successfully applied to the growth of graphene nanoribbons of diverse width and edge morphology. Here, we investigate the mechanisms driving the growth of 9-atom wide armchair graphene nanoribbons by using scanning tunneling microscopy, fast X-ray photoelectron spectroscopy, and temperature-programmed desorption techniques. Particular attention is given to the role of halogen functionalization (Br or I) of the molecular precursors. We show that the use of iodine-containing monomers fosters the growth of longer graphene nanoribbons (average length of 45 nm) due to a larger separation of the polymerization and cyclodehydrogenation temperatures. Detailed insight into the growth process is obtained by analysis of kinetic curves extracted from the fast X-ray photoelectron spectroscopy data. Our study provides fundamental details of relevance to the production of future electronic devices and highlights the importance of not only the rational design of molecular precursors but also the most suitable reaction pathways to achieve the desired final structures.
The recognition of quasicrystals, which exhibit long-range order but lack translational symmetry, represented both the introduction of a new class of materials and a transformative breakthrough in crystallography. Concomitant with the exploration of quasicrystallinity, metal-organic architectures emerged as promising and versatile systems with significant application potential. Their building principles have been studied extensively and become manifest in a multitude of intricate amorphous and crystalline phases. To date, however, indications for quasicrystalline order have been elusive in metal-organic coordination networks (MOCNs). Here we employ rare-earth-directed assembly to construct a two-dimensional tiling with quasicrystalline characteristics at a well-defined gold substrate. By careful stoichiometry control over europium centres and functional linkers, we produced a porous network, including the simultaneous expression of four-fold, five-fold and six-fold vertices. The pertaining features were directly inspected by scanning tunnelling microscopy, and the molecule-europium reticulation was recognized as square-triangle tessellation with dodecagonal symmetry. Our findings introduce quasicrystallinity in surface-confined MOCNs with a nanoporous structure and anticipate functionalities that arise from quasicrystalline ordering of the coordinative spheres.
Suitable templates to steer the formation of nanostructure arrays on surfaces are indispensable in nanoscience. Recently, atomically thin sp(2)-bonded layers such as graphene or boron nitride (BN) grown on metal supports have attracted considerable interest due to their potential geometric corrugation guiding the positioning of atoms, metallic clusters or molecules. Here, we demonstrate three specific functions of a geometrically smooth, but electronically corrugated, sp(2)/metal interface, namely, BN/Cu(111), qualifying it as a unique nanoscale template. As functional adsorbates we employed free-base porphine (2H-P), a prototype tetrapyrrole compound, and tetracyanoquinodimethane (TCNQ), a well-known electron acceptor. (i) The electronic moirons of the BN/Cu(111) interface trap both 2H-P and TCNQ, steering self-organized growth of arrays with extended molecular assemblies. (ii) We report an effective decoupling of the trapped molecules from the underlying metal support by the BN, which allows for a direct visualization of frontier orbitals by scanning tunneling microscopy (STM). (iii) The lateral molecular positioning in the superstructured surface determines the energetic level alignment; i.e., the energy of the frontier orbitals, and the electronic gap are tunable.
Acenes are an important class of polycyclic aromatic hydrocarbons which have recently gained exceptional attention due to their potential as functional organic semiconductors. Fundamentally, they are important systems to study the convergence of physico-chemical properties of all-carbon sp2-frameworks in the one-dimensional limit; and by virtue of having a zigzag edge topology they also provide a fertile playground to explore magnetism in graphenic nanostructures. The study of larger acenes is thus imperative from both a fundamental and applied perspective, but their synthesis via traditional solution-chemistry route is hindered by their poor solubility and high reactivity. Here, we demonstrate the on-surface formation of heptacene and nonacene, via visible-light-induced photo-dissociation of α-bisdiketone precursors on an Au(111) substrate under ultra-high vacuum conditions. Through combined scanning tunneling microscopy/spectroscopy and non-contact atomic force microscopy investigations, together with state-of-the-art first principles calculations, we provide insight into the chemical and electronic structure of these elusive compounds.
Nonbenzenoid carbocyclic rings are postulated to serve as important structural elements toward tuning the chemical and electronic properties of extended polycyclic aromatic hydrocarbons (PAHs, or namely nanographenes), necessitating a rational and atomically precise synthetic approach toward their fabrication. Here, using a combined bottom-up in-solution and on-surface synthetic approach, we report the synthesis of nonbenzenoid open-shell nanographenes containing two pairs of embedded pentagonal and heptagonal rings. Extensive characterization of the resultant nanographene in solution shows a low optical gap, and an open-shell singlet ground state with a low singlet–triplet gap. Employing ultra-high-resolution scanning tunneling microscopy and spectroscopy, we conduct atomic-scale structural and electronic studies on a cyclopenta-fused derivative on a Au(111) surface. The resultant five to seven rings embedded nanographene displays an extremely narrow energy gap of 0.27 eV and exhibits a pronounced open-shell biradical character close to 1 (y 0 = 0.92). Our experimental results are supported by mean-field and multiconfigurational quantum chemical calculations. Access to large nanographenes with a combination of nonbenzenoid topologies and open-shell character should have wide implications in harnessing new functionalities toward the realization of future organic electronic and spintronic devices.
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