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We synthesize artificial graphene nanoribbons by positioning carbon monoxide molecules on a copper surface to confine its surface state electrons into artificial atoms positioned to emulate the low-energy electronic structure of graphene derivatives. We demonstrate that the dimensionality of artificial graphene can be reduced to one dimension with proper "edge" passivation, with the emergence of an effectively gapped one-dimensional nanoribbon structure. These one-dimensional structures show evidence of topological effects analogous to graphene nanoribbons. Guided by first-principles calculations, we spatially explore robust, zero-dimensional topological states by altering the topological invariants of quasi-one-dimensional artificial graphene nanostructures. The robustness and flexibility of our platform allow us to toggle the topological invariants between trivial and nontrivial on the same nanostructure. Ultimately, we spatially manipulate the states to understand fundamental coupling between adjacent topological states that are finely engineered and simulate complex Hamiltonians.

For the past three decades, the coordination-driven self-assembly of three-dimensional structures has undergone rapid progress; however, parallel efforts to create large discrete two-dimensional architectures—as opposed to polymers—have met with limited success. The synthesis of metallo-supramolecular systems with well-defined shapes and sizes in the range of 10–100 nm remains challenging. Here we report the construction of a series of giant supramolecular hexagonal grids, with diameters on the order of 20 nm and molecular weights greater than 65 kDa, through a combination of intra- and intermolecular metal-mediated self-assembly steps. The hexagonal intermediates and the resulting self-assembled grid architectures were imaged at submolecular resolution by scanning tunnelling microscopy. Characterization (including by scanning tunnelling spectroscopy) enabled the unambiguous atomic-scale determination of fourteen hexagonal grid isomers. Metal-mediated self-assembly in solution typically leads to small two- and three-dimensional architectures on scales smaller than 10 nm, but now a series of large, discrete, two-dimensional supramolecular hexagonal grids have been prepared through a combination of intra- and intermolecular coordination interactions. These 20-nm-wide grids have been imaged at submolecular resolution using scanning tunnelling microscopy.

A new beamline, XTIP, has been constructed at the Advanced Photon Source to deliver monochromatic soft X-rays of between 400 and 1900 eV for the emerging synchrotron X-ray scanning tunneling microscopy technique., In recent years, there have been numerous efforts worldwide to develop the synchrotron X-ray scanning tunneling microscopy (SX-STM) technique. Here, the inauguration of XTIP, the world’s first beamline fully dedicated to SX-STM, is reported. The XTIP beamline is located at Sector 4 of the Advanced Photon Source at Argonne National Laboratory. It features an insertion device that can provide left- or right-circular as well as horizontal- and vertical-linear polarization. XTIP delivers monochromatic soft X-rays of between 400 and 1900 eV focused into an environmental enclosure that houses the endstation instrument. This article discusses the beamline system design and its performance.

During the past few decades, the study of the single polymer chain has attracted considerable attention with the goal of exploring the structure–property relationship of polymers. It still, however, remains challenging due to the variability and low atomic resolution of the amorphous single polymer chain. Here, we demonstrated a new strategy to visualize the single metallopolymer chain with a hexameric or trimeric supramolecule as a repeat unit, in which Ru(II) with strong coordination and Fe(II) with weak coordination were combined together in a stepwise manner. With the help of ultrahigh-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM) and scanning tunneling spectroscopy (STS), we were able to directly visualize both Ru(II) and Fe(II), which act as staining reagents on the repeat units, thus providing detailed structural information for the single polymer chain. As such, the direct visualization of the single random polymer chain is realized to enhance the characterization of polymers at the single-molecule level.

Despite the remarkable optical properties of rare-earth ion materials, their applications as light sources and in quantum technologies are often hindered by their long lifetimes and weak emission. Leveraging the natural compatibility of rare-earth ion molecular complexes with photonic structures, here we modify their photoluminescence properties by coupling them to a flexible open Fabry-Pérot cavity. The full in situ tunability of the Fabry-Pérot cavity allows fine control over its cavity modes and the achievement of resonant coupling between the rare-earth ion emission and the cavity modes. This configuration allows us to achieve a maximum photoluminescence enhancement factor of 30 and accelerate the decay rate up to two orders of magnitude. Our pump-power-dependent spectroscopic studies of the emitter-cavity system suggest that the cavity-modified emission is primarily caused by amplified spontaneous emission. These results suggest that integrating rare-earth ion molecular complexes with photonic structures could be a viable approach for the effective tuning of their optical properties. This natural compatibility, together with their versatile molecular structures and the resultant electronic states, renders rare-earth ion molecular complexes a potential alternative material platform for lighting and quantum applications.

The ability to control nanoscale electronic properties by introducing macroscopic strain is of critical importance for the implementation of two-dimensional (2D) materials into flexible electronics...

Using a q+ atomic force microscopy at low temperature, a sexiphenyl molecule is slid across an atomically flat Ag(111) surface along the direction parallel to its molecular axis and sideways to the axis. Despite identical contact area and underlying surface geometry, the lateral force required to move the molecule in the direction parallel to its molecular axis is found to be about half of that required to move it sideways. The origin of the lateral force anisotropy observed here is traced to the one-dimensional shape of the molecule, which is further confirmed by molecular dynamics simulations. We also demonstrate that scanning tunneling microscopy can be used to determine the comparative lateral force qualitatively. The observed one-dimensional lateral force anisotropy may have important implications in atomic scale frictional phenomena on materials surfaces.

Asymmetrical and dissymmetrical structures are widespread and play a critical role in nature and life systems. In the field of metallo-supramolecular assemblies, it is still in its infancy for constructing artificial architectures using dissymmetrical building blocks. Herein, we report the self-assembly of supramolecular systems based on two dissymmetrical double-layered ligands. With the aid of ultra-high-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM), we were able to investigate four isomeric structures corresponding to four types of binding modes of ligand LA with two major conformations complexes A. The distribution of isomers measured by STM and total binding energy of each isomer obtained by density functional theory (DFT) calculations suggested that the most abundant isomer could be the most stable one with highest total binding energy. Finally, through shortening the linker between inner and outer layers and the length of arms, the arrangement of dissymmetrical ligand LB could be controlled within one binding mode corresponding to the single conformation for complexes B.

Fluorescent metallosupramolecules have received considerable attention due to their precisely controlled dimensions as well as the tunable photophysical and photochemical properties. However, phosphorescent analogues are still rare and limited to small structures with low-temperature phosphorescence. Herein, we report the self-assembly and photophysical studies of a giant, discrete metallosupramolecular concentric hexagon functionalized with six alkynylplatinum(II) bzimpy moieties. With a size larger than 10 nm and molecular weight higher than 26 000 Da, the assembled terpyridine-based supramolecule displayed phosphorescent emission at room temperature. Moreover, the supramolecule exhibited enhanced aggregation-induced phosphorescent emission compared to the ligand by tuning the aggregation states through intermolecular interactions and significant enhancement of emission to CO

Charge density waves have been intensely studied in inorganic materials such as transition metal dichalcogenides; however their counterpart in organic materials has yet to be explored in detail. Here we report the finding of robust two-dimensional charge density waves in molecular layers formed by α-(BEDT-TTF)

Coordination-driven self-assembly has been extensively employed to construct a variety of discrete structures as a bottom-up strategy. However, mechanistic understanding regarding whether self-assembly is under kinetic or thermodynamic control is less explored. To date, such mechanistic investigation has been limited to distinct, assembled structures. It still remains a formidable challenge to study the kinetic and thermodynamic behavior of self-assembly systems with multiple assembled isomers due to the lack of characterization methods. Herein, we use a stepwise strategy which combined self-recognition and self-assembly processes to construct giant metallo-supramolecules with 8 positional isomers in solution. With the help of ultrahigh-vacuum, low-temperature scanning tunneling microscopy and scanning tunneling spectroscopy, we were able to unambiguously differentiate 14 isomers on the substrate which correspond to 8 isomers in solution. Through measurement of 162 structures, the experimental probability of each isomer was obtained and compared with the theoretical probability. Such a comparison along with density functional theory (DFT) calculation suggested that although both kinetic and thermodynamic control existed in this self-assembly, the increased experimental probabilities of isomers compared to theoretical probabilities should be attributed to thermodynamic control.

Molecular flexure, and molecule-metal contact of para-sexiphenyl molecules on a Ag(111) surface are investigated by using low temperature scanning tunneling microscopy, and molecular manipulations. Atom trapping with sexiphenyl molecules is realized by laterally manipulating the molecules onto individual silver atoms and up to three silver atoms have been trapped. We also demonstrate breaking of a silver dimer into individual silver atoms by atom trapping. STM manipulation experiments show that the molecule-metal complexes formed by the atom trapping are mechanically stable. Moreover, Lateral manipulation of a single sexiphenyl across a Ag(111) atomic step highlights how the molecule moves across step-edges; the molecule can easily conform across the step and it recovers original configuration after the manipulation.

We elucidate the structure of assemblies formed by three conjugated molecules with very similar chemical structure, differing only by two fluorine atoms, on an Ag 111 surface to gain insight into the intricate interplay of attractive and repulsive interactions that govern the self assembly of molecules on a metal surface. With scanning tunneling microscopy we observe substantially different self assembled structures for sub monolayers of parasexiphenyl 6P and its two partially fluorinated derivatives ortho 2F 6P and meta 2F 6P see Fig. 1 , which we can fully rationalize only with state of the art density functional theory modeling. By deliberate discriminating all involved interactions, that is, electrostatic due to permanent charges, polarization and dispersion, as well as hydrogen bonding, we can provide new insights for advanced self assembly strategies. We demonstrate that fluorination at selected positions of conjugated molecules provides for sufficiently strong, yet nonrigid, H F bonding capability to circumvent dominating repulsive interactions at very low molecular surface coverage. This enables the realization and steering of individual and stable nanoscale molecular assemblies as well as their study, without the need to approach monolayer coverage, which could substantially alter the obtained structure. Furthermore, the insight provided here helps to understand how fluorine substitution in conjugated molecules and polymers contributes to thin film and bulk structures, which, in turn will enable realizing organic electronic materials with superior optical and charge transport properties for electronic and optoelectronic applications

Carotenoids and chlorophyll are essential parts of plant leaves and are involved in photosynthesis, a vital biological process responsible for the origin of life on Earth. Here, we investigate how β-carotene and chlorophyll-a form mixed molecular phases on a Au(111) surface using low-temperature scanning tunneling microscopy and molecular manipulation at the single-molecule level supported by density functional theory calculations. By isolating individual molecules from nanoscale molecular clusters with a scanning tunneling microscope tip, we are able to identify five β-carotene conformations including a structure exhibiting a three-dimensional conformation. Furthermore, molecular resolution images enable direct visualization of β-carotene/chlorophyll-a clsuters, with intimate structural details highlighting how they pair: β-carotene preferentially positions next to chlorophyll-a and induces switching of chlorophyll-a from straight to several bent tail conformations in the molecular clusters.

Charge density waves and negative differential resistance are seemingly unconnected physical phenomena. The former is an ordered quantum fluid of electrons, intensely investigated for its relation with superconductivity, while the latter receives much attention for its potential applications in electronics. Here we show that these two phenomena can not only coexist but also that the localized electronic states of the charge density wave are essential to induce negative differential resistance in a transition metal dichalcogenide, 1T-TaS2. Using scanning tunneling microscopy and spectroscopy, we report the observation of negative differential resistance in the commensurate charge density wave state of 1T-TaS2. The observed phenomenon is explained by the interplay of interlayer and intra-layer tunneling with the participation of the atomically localized states of the charge density wave maxima and minima. We demonstrate that lattice defects can locally affect the coupling between the layers and are therefore a mechanism to realize NDR in these materials.

Using temperature-dependent and low-frequency Raman spectroscopy, we address the question of how the transition from bulk to a few atomic layers affects the charge density wave (CDW) phases in $1T\text{\ensuremath{-}}\mathrm{Ta}{\mathrm{S}}_{2}$. We find that for crystals with thickness larger than $\ensuremath{\approx}10$ nm the transition temperatures between the different phases as well as the hysteresis that occurs in the thermal cycle correspond to the ones expected for a bulk sample. However, when the crystals become thinner than $\ensuremath{\approx}10$ nm, the low-temperature commensurate CDW phases can be suppressed down to the experimentally accessible temperatures ($\ensuremath{\sim}80$ K) upon cooling at moderate rates $(\ensuremath{\sim}5\phantom{\rule{0.16em}{0ex}}\mathrm{K}\phantom{\rule{0.16em}{0ex}}\mathrm{mi}{\mathrm{n}}^{\ensuremath{-}1})$. In addition, even the near commensurate CDW phase is not accessible in few-layer flakes below $\ensuremath{\approx}4$ nm for even slower cooling rates $(\ensuremath{\sim}1\phantom{\rule{0.16em}{0ex}}\mathrm{K}\phantom{\rule{0.16em}{0ex}}\mathrm{mi}{\mathrm{n}}^{\ensuremath{-}1})$. We employ Raman hyperspectral imaging to statistically confirm these findings and consider the interlayer coupling and its dynamics to play significant roles in determining the properties of CDW systems consisting of a few unit cells in the vertical direction.

Multicomponent self-assembly in one pot provides an efficient way for constructing complex architectures using multiple types of building blocks with different levels of interactions orthogonally. The preparation of multiple types of building blocks typically includes tedious synthesis. Here, we developed a multicomponent synthesis/self-assembly strategy, which combined covalent interaction (C-N bond, formed through condensation of pyrylium salt with primary amine) and metal-ligand interaction (N → Zn bond, formed through 2,2':6',2″-terpyridine-Zn coordination) in one pot. The high compatibility of this pair of interactions smoothly and efficiently converted three and four types of components into the desired complex structures, which are supramolecular Kandinsky Circles and spiderwebs, respectively.

Two-dimensional (2D) materials provide a plethora of novel condensed matter physics and are the new playground in materials science, offering potentially vast applications. One of the critical hurdles for many 2D systems is the synthesis of these low-dimensional systems as well as the prediction and identification of new candidates. Herein, a self-assembly of a monolayer tellurene by bonding CdTe wafers is demonstrated for the first time. The conventional applications of wafer-bonding range from the production of microelectromechanical systems to the synthesis of lattice-mismatched multi-junction photovoltaics. Due to the heterogeneous materials that are typically employed, the bond-interface usually contains a thin amorphous layer or arrays of dislocations. Such an interface is thus itself inactive and in many cases has detrimental effects on the device. The new material phase stabilized in this work consists of an undulating monolayer of tellurium atoms covalently bonded to {111} Cd-terminated CdTe wafer surfaces. First-principles calculations and experimentally observed changes in the localized plasmon excitation energy indicate the clear rearrangement of the underlying band-structure suggesting a metallic character, bands showing linear dispersion, and a significant asymmetric spin-band splitting. The I–V characteristics show the presence of a highly conductive pathway that lowers the resistivity by three orders of magnitude, as compared to bulk CdTe, which can be attributed to the tellurium monolayer. The findings indicate that suitably chosen crystallographic wafer surfaces can act as structural templates allowing the production of exotic phases. The presently stabilized monolayer is an addition to the family of tellurene variants, providing new insights into the fundamental properties of this and other emerging 2D materials, while attracting attention to the unusual side of the wafer-bonding technology exemplified in this study.

X-ray beam-induced damage in nanoscale metal islands was investigated. Monolayer-high Ni islands were prepared on a Cu(111) substrate. High brilliance X-rays with photon energies between 8.45 and 8.85 keV illuminated the sample for about 11 hours. In order to track changes in the morphology of the islands, the synchrotron X-ray scanning tunneling microscopy (SX-STM) technique was utilized. The result shows that X-ray illumination onto Ni islands does not induce noticeable damage. The study demonstrates that local beam-induced changes can be studied using SX-STM.

Kondo resonances in heterostructures formed by magnetic molecules on a metal require free host electrons to interact with the molecular spin and create delicate many-body states. Unlike graphene, semiconducting graphene nanoribbons do not have free electrons due to their large bandgaps, and thus they should electronically decouple molecules from the metal substrate. Here, we observe unusually well-defined Kondo resonances in magnetic molecules separated from a gold surface by graphene nanoribbons in vertically stacked heterostructures. Surprisingly, the strengths of Kondo resonances for the molecules on graphene nanoribbons appear nearly identical to those directly adsorbed on the top, bridge and threefold hollow sites of Au(111). This unexpectedly strong spin-coupling effect is further confirmed by density functional calculations that reveal no spin–electron interactions at this molecule-gold substrate separation if the graphene nanoribbons are absent. Our findings suggest graphene nanoribbons mediate effective spin coupling, opening a way for potential applications in spintronics., Semiconducting graphene nanoribbon provides a platform for band-gap engineering desired for electronic and optoelectronic applications. Here, Li et al. show that graphene nanoribbon can effectively mediate the interaction of molecular magnetic moment and electronic spin in underlying metallic substrates.

9-(Bis-p-tert-octylphenyl)-amino-perylene-3,4-dicarboxy anhydride (BOPA-PDCA) is a strongly dipolar molecule representing a group of asymmetrically substituted perylenes that are employed in dye-sensitized solar cells and hold great promise for discotic liquid crystal applications. Thin BOPA-PDCA films with orientated dipole moments can potentially be used to tune the energy-level alignment in electronic devices and store information. To help assessing these prospects, we here elucidate the molecular self-assembly and electronic structure of BOPA-PCDA employing room temperature scanning tunneling microscopy and spectroscopy in combination with ultraviolet and X-ray photoelectron spectroscopies. BOPA-PCDA monolayers on Au(111) exclusively form in-plane antiferroelectric phases. The molecular arrangements, the increase of the average number of molecules per unit cell via ripening, and the rearrangement upon manipulation with the STM tip indicate an influence of the dipole moment on the molecular assembly and the rearrangement. A slightly preferred out-of-plane orientation of the molecules in the multilayer induces a surface potential of 1.2 eV. This resembles the giant surface potential effect that was reported for vacuum-deposited tris(8-hydroxyquinoline)aluminum and deemed applicable for data storage. Notably, the surface potential in the case of BOPA-PDCA can in part be reversibly removed by visible light irradiation.

A tunneling smart tip of a synchrotron X-ray scanning tunneling microscope provides simultaneously localized topographic, elemental and magnetic information., Localized spectroscopy with simultaneous topographic, elemental and magnetic information is presented. A synchrotron X-ray scanning tunneling microscope has been employed for the local study of the X-ray magnetic circular dichroism at the Fe L 2,3-edges of a thin iron film grown on Cu(111). Polarization-dependent X-ray absorption spectra have been obtained through a tunneling smart tip that serves as a photoelectron detector. In contrast to conventional spin-polarized scanning tunneling microscopy, X-ray excitations provide magnetic contrast even with a non-magnetic tip. Intensity variations in the photoexcited tip current point to chemical variations within a single magnetic Fe domain.

In the continuously growing field of correlated electronic molecular crystals, there is significant interest in addressing alkali-metal-intercalated aromatic hydrocarbons, in which the possibility of high-temperature superconductivity emerges. However, searching for superconducting aromatic molecular crystals remains elusive due to their small shielding fraction volume. To exploit this potential, a design principle for percolation networks of technologically important film geometry is indispensable. Here the effect of potassium-intercalation is shown on the percolation network in self-assembled aromatic molecular crystals. It is demonstrated that one-dimensional (1D) dipole pairs, induced by dipole interaction, regulate the conductivity, as well as the electronic and optical transitions, in alkali-metal-intercalated molecular electronic crystals. A solid-solution growth methodology of aromatic molecular films with a broad range of stability is developed to uncover electronic and optical transitions of technological importance. The light-induced electron interactions enhance the charge-carrier itinerancy, leading to a switchable metal-to-insulator transition. This discovery opens a route for the development of aromatic molecular electronic solids and long-term modulation of electronic efficacy in nanotechnologically important thin films.

Magnetism at buried interfaces plays a crucial role in many emerging phenomena, but detection of interfacial magnetism in close proximity to a surface with elemental and chemical sensitivity is a challenging task. Here, we use low temperature synchrotron x-ray scanning tunneling microscopy to investigate x-ray magnetic circular dichroism and the near edge x-ray absorption fine structure of La0.67Sr0.33MnO3-LaNiO3 superlattices. In stark contrast to the weak magnetic signal of Mn when the La0.67Sr0.33MnO3 layers are located on top, a robust x-ray magnetic circular dichroism signal is detected when they are buried underneath the LaNiO3 layers. The near edge x-ray absorption fine structure reveals the valence states of manganese, while the oxygen K-edge x-ray absorption spectra show an increase in hole formation, indicating a cogent charge transfer at the LaNiO3/La0.67Sr0.33MnO3 interface. This work demonstrates that scanning tunneling microscopy can be extended to the synchrotron X-ray study of buried interfaces by controlling the tip-sample separation in the nanometer regime.

High-speed beam choppers are a crucial part of time-resolved x-ray studies as well as a necessary component to enable elemental contrast in synchrotron x-ray scanning tunneling microscopy (SX-STM). However, many chopper systems are not capable of operation in vacuum, which restricts their application to x-ray studies with high photon energies, where air absorption does not present a significant problem. To overcome this limitation, we present a fully ultra-high vacuum (UHV) compatible chopper system capable of operating at variable chopping frequencies up to 4 kHz. The lightweight aluminum chopper disk is coated with Ti and Au films to provide the required beam attenuation for soft and hard x-rays with photon energies up to about 12 keV. The chopper is used for lock-in detection of x-ray enhanced signals in SX-STM.

A range of artificial molecular systems has been created that can exhibit controlled linear and rotational motion. In the further development of such systems, a key step is the addition of communication between molecules in a network. Here, we show that a two-dimensional array of dipolar molecular rotors can undergo simultaneous rotational switching when applying an electric field from the tip of a scanning tunnelling microscope. Several hundred rotors made from porphyrin-based double-decker complexes can be simultaneously rotated when in a hexagonal rotor network on a Cu(111) surface by applying biases above 1 V at 80 K. The phenomenon is observed only in a hexagonal rotor network due to the degeneracy of the ground-state dipole rotational energy barrier of the system. Defects are essential to increase electric torque on the rotor network and to stabilize the switched rotor domains. At low biases and low initial rotator angles, slight reorientations of individual rotors can occur, resulting in the rotator arms pointing in different directions. Analysis reveals that the rotator arm directions are not random, but are coordinated to minimize energy via crosstalk among the rotors through dipolar interactions. Hundreds of molecular rotors in a 2D network can be simultaneously rotated by applying an electric field from the tip of a scanning tunnelling microscope.

Engineering of supramolecular assemblies on surfaces is an emerging field of research impacting chemistry, electronics, and biology. Among supramolecular assemblies, metal-containing structures provide rich properties and enable robust nanostructured designs. In this issue of ACS Nano, Feng et al. report that supramolecular assemblies can trap gold adatoms that maintain a charged state on a Au(111) surface. Such charged adatoms may offer additional degrees of freedom in designing novel supramolecular architectures for efficient catalysts, memory, and charge storage for medical applications.