Transmetalation in Surface-Confined Single-Layer Organometallic Networks with Alkynyl-Metal-Alkynyl Linkages.

Transmetalation represents an appealing strategy toward fabricating and tuning functional metal-organic polymers and frameworks for diverse applications. In particular, building two-dimensional metal-organic and organometallic networks affords versatile nanoarchitectures of potential interest for nanodevices and quantum technology. The controlled replacement of embedded metal centers holds promise for exploring versatile material varieties by serial modification and different functionalization.

Analogous electronic states in graphene and planer metallic quantum dots.

Graphene nanostructures offer wide range of applications due to their distinguished and tunable electronic properties. Recently, atomic and molecular graphene were modeled following simple free-electron scattering by periodic muffin tin potential leading to remarkable agreement with density functional theory. Here we extend the analogy of the -electronic structures and quantum effects between atomic graphene quantum dots (QDs) and homogeneous planer metallic counterparts of similar size and shape.

Unconventional Band Structure via Combined Molecular Orbital and Lattice Symmetries in a Surface-Confined Metallated Graphdiyne Sheet.

Graphyne (GY) and graphdiyne (GDY)-based monolayers represent the next generation 2D carbon-rich materials with tunable structures and properties surpassing those of graphene. However, the detection of band formation in atomically thin GY/GDY analogues has been challenging, as both long-range order and atomic precision have to be fulfilled in the system. The present work reports direct evidence of band formation in on-surface synthesized metallated Ag-GDY sheets with mesoscopic (≈1 µm) regularity.

Deceptive orbital confinement at edges and pores of carbon-based 1D and 2D nanoarchitectures.

The electronic structure defines the properties of graphene-based nanomaterials. Scanning tunneling microscopy/spectroscopy (STM/STS) experiments on graphene nanoribbons (GNRs), nanographenes, and nanoporous graphene (NPG) often determine an apparent electronic orbital confinement into the edges and nanopores, leading to dubious interpretations such as image potential states or super-atom molecular orbitals. We show that these measurements are subject to a wave function decay into the vacuum that masks the undisturbed electronic orbital shape.

Ultraconfined Plasmons in Atomically Thin Crystalline Silver Nanostructures.

The ability to confine light down to atomic scales is critical for the development of applications in optoelectronics and optical sensing as well as for the exploration of nanoscale quantum phenomena. Plasmons in metallic nanostructures with just a few atomic layers in thickness can achieve this type of confinement, although fabrication imperfections down to the subnanometer scale hinder actual developments. Here, narrow plasmons are demonstrated in atomically thin crystalline silver nanostructures fabricated by prepatterning silicon substrates and epitaxially depositing silver films of just a few atomic layers in thickness.

Formation of an Extended Quantum Dot Array Driven and Autoprotected by an Atom-Thick -BN Layer.

Engineering quantum phenomena of two-dimensional nearly free electron states has been at the forefront of nanoscience studies ever since the first creation of a quantum corral. Common strategies to fabricate confining nanoarchitectures rely on manipulation or on applying supramolecular chemistry principles. The resulting nanostructures do not protect the engineered electronic states against external influences, hampering the potential for future applications.

Engineering novel surface electronic states complex supramolecular tessellations.

Tailoring Shockley surface-state (SS) electrons utilizing complex interfacial supramolecular tessellations was explored by low-temperature scanning tunnelling microscopy and spectroscopy, combined with computational modelling using electron plane wave expansion (EPWE) and empirical tight-binding (TB) methods. Employing a recently introduced gas-mediated on-surface reaction protocol, three distinct types of open porous networks comprising paired organometallic species as basic tectons were selectively synthesized. In particular, these supramolecular networks feature semiregular Archimedean tilings, providing intricate quantum dots (QDs) coupling scenarios compared to hexagonal porous superlattices.

Atomically-Precise Texturing of Hexagonal Boron Nitride Nanostripes.

Monolayer hexagonal boron nitride (hBN) is attracting considerable attention because of its potential applications in areas such as nano- and opto-electronics, quantum optics and nanomagnetism. However, the implementation of such functional hBN demands precise lateral nanostructuration and integration with other two-dimensional materials, and hence, novel routes of synthesis beyond exfoliation. Here, a disruptive approach is demonstrated, namely, imprinting the lateral pattern of an atomically stepped one-dimensional template into a hBN monolayer.

Near Fermi Superatom State Stabilized by Surface State Resonances in a Multiporous Molecular Network.

Two-dimensional honeycomb molecular networks confine a substrate's surface electrons within their pores, providing an ideal playground to investigate the quantum electron scattering phenomena. Besides surface state confinement, laterally protruding organic states can collectively hybridize at the smallest pores into superatom molecular orbitals. Although both types of pore states could be simultaneously hosted within nanocavities, their coexistence and possible interaction are unexplored.

Metallic bands in chevron-type polyacenes.

We present electronic structure calculations based on a single-parameter plane wave expansion method for basic graphene building blocks, namely -oligophenylenes and -oligoacenes, revealing excellent agreement with density-functional theory. When oligophenylene molecules are joined through (zigzag) or (chevron) junctions, the resulting molecular dimers and polymers exhibit a semiconducting character. While zigzag dimers of oligoacenes also exhibit gapped electronic structures, their chevron-phase features a sharp metallic band at the Fermi energy.

Electron Transmission through Coordinating Atoms Embedded in Metal-Organic Nanoporous Networks.

On-surface metal-organic nanoporous networks generally refer to adatom coordinated molecular arrays, which are characterized by the presence of well-defined and regular nanopores. These periodic structures constructed using two types of components confine the surface electrons of the substrate within their nanocavities. However, the confining (or scattering) strength that individual building units exhibit is a priori unknown.

Surface state tunable energy and mass renormalization from homothetic quantum dot arrays.

Quantum dot arrays in the form of molecular nanoporous networks are renowned for modifying the electronic surface properties through quantum confinement. Here we show that, compared to the pristine surface state, the band bottom of the confined states can exhibit downward shifts accompanied by a lowering of the effective masses simultaneous to the appearance of tiny gaps at the Brillouin zone boundaries. We observed these effects by angle resolved photoemission for two self-assembled homothetic (scalable) Co-coordinated metal-organic networks.

Controlling the stereospecific bonding motif of Au-thiolate links.

Over the last decades, organosulfur compounds at the interface of noble metals have proved to be extremely versatile systems for both fundamental and applied research. However, the anchoring of thiols to gold remained an object of controversy for a long time. The RS-Au-SR linkage, in particular, is a robust bonding configuration that displays interesting properties.

Plasmonics in Atomically Thin Crystalline Silver Films.

Light-matter interaction at the atomic scale rules fundamental phenomena such as photoemission and lasing while enabling basic everyday technologies, including photovoltaics and optical communications. In this context, plasmons, the collective electron oscillations in conducting materials, are important because they allow the manipulation of optical fields at the nanoscale. The advent of graphene and other two-dimensional crystals has pushed plasmons down to genuinely atomic dimensions, displaying appealing properties such as a large electrical tunability.

Electronic Structure Tunability by Periodic meta-Ligand Spacing in One-Dimensional Organic Semiconductors.

Designing molecular organic semiconductors with distinct frontier orbitals is key for the development of devices with desirable properties. Generating defined organic nanostructures with atomic precision can be accomplished by on-surface synthesis. We use this "dry" chemistry to introduce topological variations in a conjugated poly( para-phenylene) chain in the form of meta-junctions.

Precise engineering of quantum dot array coupling through their barrier widths.

Quantum dots are known to confine electrons within their structure. Whenever they periodically aggregate into arrays and cooperative interactions arise, novel quantum properties suitable for technological applications show up. Control over the potential barriers existing between neighboring quantum dots is therefore essential to alter their mutual crosstalk.

Robust surface doping of Bi2Se3 by rubidium intercalation.

Rubidium adsorption on the surface of the topological insulator Bi(2)Se(3) is found to induce a strong downward band bending, leading to the appearance of a quantum-confined two-dimensional electron gas state (2DEG) in the conduction band. The 2DEG shows a strong Rashba-type spin-orbit splitting, and it has previously been pointed out that this has relevance to nanoscale spintronics devices. The adsorption of Rb atoms, on the other hand, renders the surface very reactive, and exposure to oxygen leads to a rapid degrading of the 2DEG.