Graphene nanoribbons (GNRs) are of enormous research interest as a promising active component in electronic devices, for example, field-effect transistors (FET). The recently developed "bottomup" on-surface synthesis provides an unprecedented approach for the generation of GNRs on metal surfaces with atomic precision. In order to fabricate well-defined GNRs on surfaces, numerous previous works have been focused on the delicate engineering of building blocks. Lateral fusion of polyphenylene chains into GNRs, as a more flexible method, now has received an increasing attention. However, the lateral fusion into GNRs reported to date is merely limited to the straight GNRs. The GNRs with other topologies potentially displaying distinctive electronic properties are rarely reported. In this work, we report the synthesis of armchair-edged graphene nanoribbons (AGNRs) with zigzag topology for the first time via a stepwise polymerization reaction starting from 4,4″-dibromo-m-terphenyl (DMTP) precursor on Au(111). Self-assembled unreacted monomers, covalent dimers, and zigzag polyphenylene chains are observed at different temperatures. Various GNRs with zigzag topology, including 6-AGNRs, 9-AGNRs, and nanoporous AGNRs are eventually produced through lateral fusion of polyphenylene chains. This study further diversifies the GNR family. Confining the zigzag polyphenylene chains in an ideal arrangement for subsequent lateral fusion can be explored in the future.
Macrocycles have attracted much attention due to their specific "endless" topology, which results in extraordinary properties compared to related linear (open-chain) molecules. However, challenges still remain in their controlled synthesis with well-defined constitution and geometry. Here, we report the successful application of the (pseudo-)high-dilution method to the conditions of on-surface synthesis in ultrahigh vacuum. This approach leads to high yields (up to 84%) of cyclic hyperbenzene ([18]-honeycombene) via an Ullmann-type reaction from 4,4″-dibromo-meta-terphenyl (DMTP) as precursor on a Ag(111) surface. The mechanism of macrocycle formation was explored in detail using scanning tunneling microscopy and X-ray photoemission spectroscopy. We propose that the dominant pathway for hyperbenzene (MTP) formation is the stepwise desilverization of an organometallic (MTP-Ag) macrocycle, which forms via cyclization of (MTP-Ag) chains under pseudo-high-dilution conditions. The high probability of cyclization on the stage of the organometallic phase results from the reversibility of the C-Ag bond. The case is different from that in solution, in which cyclization typically occurs on the stage of a covalently bonded open-chain precursor. This difference in the cyclization mechanism on a surface compared to that in solution stems mainly from the 2D confinement exerted by the surface template, which hinders the flipping of chain segments necessary for cyclization.
The bottom-up construction of low-dimensional macromolecular nanostructures directly on a surface is a promising approach for future application in molecular electronics and integrated circuit production. However, challenges still remain in controlling the formation of these nanostructures with predetermined patterns (such as linear or cyclic) or dimensions (such as the length of one-dimensional (1D) chains). Here, we demonstrate that a high degree of structural control can be achieved by employing a Cu(110)-(2×1)O nanotemplate for the confined synthesis of organometallic chains and macrocycles. This template contains ordered arrays of alternating stripes of Cu-O chains and bare Cu, the widths of which are controllable. Using scanning tunneling microscopy and low-energy electron diffraction, we show that well-defined, ordered 1D zigzag organometallic oligomeric chains with uniform lengths can be fabricated on the Cu stripes (width >5.6 nm) of the Cu(110)-(2×1)O surface. In addition, the lengths of the meta-terphenyl (MTP)-based chains can be adjusted by controlling the widths of the Cu stripes within a certain range. When reducing the widths of Cu stripes to a range of 2.6 to 5.6 nm, organometallic macrocycles including tetramer (MTP-Cu)4, hexamer (MTP-Cu)6, and octamer (MTP-Cu)8 species are formed due to the spatial confinement effect and attraction to the Cu-O chains. An overview of all formed organometallic macrocycles on the Cu stripes with different widths reveals that the origin of the formation of these macrocycles is the cis-configured organometallic dimer (MTP)2Cu3, which was observed on the extremely narrow Cu stripe with a width of 1.5 nm.
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