On-surface synthesis of aromatic cyclo[10]carbon and cyclo[14]carbon.

All-carbon materials based on sp2-hybridized atoms, such as fullerenes1, carbon nanotubes2 and graphene3, have been much explored due to their remarkable physicochemical properties and potential for applications. Another unusual all-carbon allotrope family are the cyclo[n]carbons (Cn) consisting of two-coordinated sp-hybridized atoms. They have been studied in the gas phase since the twentieth century4-6, but their high reactivity has meant that condensed-phase synthesis and real-space characterization have been challenging, leaving their exact molecular structure open to debate7-11. Only in 2019 was an isolated C18 generated on a surface and its polyynic structure revealed by bond-resolved atomic force microscopy12,13, followed by a recent report14 on C16. The C18 work trigged theoretical studies clarifying the structure of cyclo[n]carbons up to C100 (refs. 15-20), although the synthesis and characterization of smaller Cn allotropes remains difficult. Here we modify the earlier on-surface synthesis approach to produce cyclo[10]carbon (C10) and cyclo[14]carbon (C14) via tip-induced dehalogenation and retro-Bergman ring opening of fully chlorinated naphthalene (C10Cl8) and anthracene (C14Cl10) molecules, respectively. We use atomic force microscopy imaging and theoretical calculations to show that, in contrast to C18 and C16, C10 and C14 have a cumulenic and cumulene-like structure, respectively. Our results demonstrate an alternative strategy to generate cyclocarbons on the surface, providing an avenue for characterizing annular carbon allotropes for structure and stability.

Local Chiral Inversion of Thymine Dimers by Manipulating Single Water Molecules.

Water, as one of the most important and indispensable small molecules in vivo, plays a crucial role in driving biological self-assembly processes. Real-space detection and identification of water-induced organic structures and further capture of dynamic dehydration processes are important yet challenging, which would help to reveal the cooperation and competition mechanisms among water-involved noncovalent interactions. Herein, introduction of water molecules onto the self-assembled thymine (T) structures under ultrahigh vacuum (UHV) conditions results in the hydration of hydrogen-bonded T dimers forming a well-ordered water-involved T structure. Reversibly, a local dehydration process is achieved by in situ scanning tunneling microscopy (STM) manipulation on single water molecules, where the adjacent T dimers connected with water molecules undergo a local chiral inversion process with the hydrogen-bonding configuration preserved. Such a strategy enables real-space identification and detection of the interactions between water and organic molecules, which may also shed light on the understanding of biologically relevant self-assembly processes driven by water.

On-surface synthesis and characterization of polyynic carbon chains.

Carbyne, an elusive sp-hybridized linear carbon allotrope, has fascinated chemists and physicists for decades. Due to its high chemical reactivity and extreme instability, carbyne was much less explored in contrast to the sp2-hybridized carbon allotropes such as graphene. Herein, we report the on-surface synthesis of polyynic carbon chains by demetallization of organometallic polyynes on the Au(111) surface; the longest one observed consists of ∼60 alkyne units (120 carbon atoms). The polyynic structure of carbon chains with alternating triple and single bonds was unambiguously revealed by bond-resolved atomic force microscopy. Moreover, an atomically precise polyyne, C14, was successfully produced via tip-induced dehalogenation and ring-opening of the decachloroanthracene molecule (C14Cl10) on a bilayer NaCl/Au(111) surface at 4.7 K, and a band gap of 5.8 eV was measured by scanning tunnelling spectroscopy, in a good agreement with the theoretical HOMO-LUMO gap (5.48 eV).

On-surface synthesis and characterization of anti-aromatic cyclo[12]carbon and cyclo[20]carbon.

Cyclo[n]carbons have recently attracted significant attention owing to their geometric and electronic structures remaining largely unexplored in the condensed phase. In this work, we focus on two anti-aromatic cyclocarbons, namely C12 and C20. By designing two fully halogenated molecular precursors both including 4-numbered rings, we further extend the on-surface retro-Bergman ring-opening reaction, and successfully produce C12 and C20. The polyynic structures of C12 and C20 are unambiguously revealed by bond-resolved atomic force microscopy. More importantly, subtly positioning the C20 molecule into an atomic fence formed by Cl clusters allows us to experimentally probe its frontier molecular orbitals, yielding a transport gap of 3.8 eV measured from scanning tunneling spectroscopy. Our work may advance the field by easier synthesis of a series of cyclocarbons via on-surface retro-Bergman ring-opening strategy.

On-Surface Synthesis of a Carbon Nanoribbon Composed of 4-5-6-8-Membered Rings.

From the structure point of view, there are a number of ways of tiling a carbon sheet with different polygons, resulting in prospects of tailoring electronic structures of low-dimensional carbon nanomaterials. However, up to now, the experimental fabrication of such structures embedded with periodic nonhexagon carbon polygons, especially ones with more than three kinds, is still very challenging, leaving their potential properties unexplored. Here we report the bottom-up synthesis of a nanoribbon composed of 4-5-6-8-membered rings via lateral fusion of polyfluorene chains on Au(111). Scanning probe microscopy unequivocally determines both the geometric structure and the electronic properties of such a nanoribbon, revealing its semiconducting property with a bandgap of ∼1.4 eV on Au(111). We expect that this work could be helpful for designing and synthesizing complicated carbon nanoribbons.

Formation of Unconventional Stoichiometric Na-Cl Magic-Number Nanoclusters and 2D Assembly on Ir(111).

Sodium chlorides in non-1:1 stoichiometry are counterintuitive but recently their existence has been found under the high pressure condition or in the confined space between graphene sheets. Here the direct observation of the formation of Na3 Cl nanoclusters, a stable magic-number structure, is reported on an Ir(111) surface using scanning tunneling microscopy and noncontact atomic force microscopy. The stability of Na3 Cl nanoclusters in the free and adsorbed state is corroborated by density functional theory calculations. It is also found that a density of nanoclusters together with Cl adatoms may further aggregate and self-assemble into a Na3 Cl4 monolayer, forming a novel metastable phase of NaCl(111) with a honeycomb lattice. Further calculations suggest that charge transfer between the polar nanoclusters and the metal substrate stabilizes NaCl of non-1:1 stoichiometry. The work exhibits the possibility of exploring unconventional ionic crystals on the surface with atomically precise control of structure and composition.

Water-Induced Chiral Separation on a Au(111) Surface.

Facing the scientific question of the origin of chirality in life, water is considered to play a crucial role in driving many biologically relevant processes in vivo. Water has been demonstrated in vitro to be related to chiral generation, amplification, and inversion, while the underlying mechanism is still not fully understood. Real-space evidence at the single-molecule level is thus urgently required to understand the role of water molecules in biomolecular chirality related issues. Herein, we choose one of the RNA bases, the biomolecule uracil (U), which self-assembles into racemic hydrogen-bonded structures. Upon water exposure, surprisingly, racemic structures could be transformed to homochiral water-involved structures, resulting in an unexpected chiral separation on the surface. The origin of chiral separation is due to preferential binding between water and the specific site of U molecules, which leads to the formation of the energetically most favorable homochiral (U-H2O-U)2 cluster as seed for subsequent chiral amplification. Such a water-driven self-assembly process may also be extended to other biologically relevant systems such as amino acids and sugars, which would provide general insights into the role that water molecules may play in the origin of homochirality in vivo.

Structural Phase Transitions of Molecular Self-Assembly Driven by Nonbonded Metal Adatoms.

The involvement of metal atoms in molecular assemblies has enriched the structural and functional diversity of two-dimensional supramolecular networks, where metal atoms are incorporated into the architecture via coordination or ionic bonding. Here we present a temperature-variable study of the self-assembly of the 1,3,5-tribromobenzene (TriBB) molecule on Cu(111) that reveals the involvement of nonbonded adatoms in the molecular matrix. By means of scanning tunneling microscopy and noncontact atomic force microscopy, we demonstrate the molecular-level details of a phase transition of TriBB assembly from the close-packed to porous honeycomb structures at 78 K. This is an unexpected transformation because the close-packed phase is thermodynamically favored in view of its higher molecular density and more intermolecular bonds as compared to the honeycomb lattice. A comprehensive density functional theory calculation suggests that Cu adatoms should be involved in the formation of the honeycomb network, where the Cu adatoms help stabilize the molecular assembly via enhanced van der Waals interactions between TriBB molecules and the underlying substrate. Both calculation and experimental results suggest no chemical bonding or direct charge transfer between the adatoms and the molecules, thus the electronic characteristics of the Cu adatoms trapped in the molecular confinement are close to the intrinsic ones on a clean metal surface and different from those in the traditional coordination-bonded framework. The nonbonded metal adatoms embedded self-assemblies may complement the metal-organic coordination system and can be used to tailor the chemical reactivity and electronic properties of supramolecular structures.