Direct imaging of the induced‐fit effect in molecular self‐assembly

Molecular recognition is a crucial driving force for molecular self‐assembly. In many cases molecules arrange in the lowest energy configuration following a lock‐and‐key principle. When molecular flexibility comes into play, the induced‐fit effect may govern the self‐assembly. Here, the self‐assembly of dicyanovinyl‐hexathiophene (DCV6T) molecules, a prototype specie for highly efficient organic solar cells, on Au(111) by using low‐temperature scanning tunneling microscopy and atomic force microscopy is investigated. DCV6T molecules assemble on the surface forming either islands or chains. In the islands the molecules are straight—the lowest energy configuration in gas phase—and expose the dicyano moieties to form hydrogen bonds with neighbor molecules. In contrast, the structure of DCV6T molecules in the chain assemblies deviates significantly from their gas‐phase analogues. The seemingly energetically unfavorable bent geometry is enforced by hydrogen‐bonding intermolecular interactions. Density functional theory calculations of molecular dimers quantitatively demonstrate that the deformation of individual molecules optimizes the intermolecular bonding structure. The intermolecular bonding energy thus drives the chain structure formation, which is an expression of the induced‐fit effect

Charge tedistribution and transport in molecular contacts

Under the terms of the Creative Commons Attribution License 3.0 (CC-BY).-- et al.The forces between two single molecules brought into contact, and their connection with charge transport through the molecular junction, are studied here using non contact AFM, STM, and density functional theory simulations. A carbon monoxide molecule approaching an acetylene molecule (C2H2) initially feels weak attractive electrostatic forces, partly arising from charge reorganization in the presence of molecular. We find that the molecular contact is chemically passive, and protects the electron tunneling barrier from collapsing, even in the limit of repulsive forces. However, we find subtle conductance and force variations at different contacting sites along the C2H2 molecule attributed to a weak overlap of their respective frontier orbitals.The research was supported by DFG (Grant No. Sfb 658), the Czech Science Foundation (GAČR) Project No. 14-02079S, GAAV Grant No. M100101207, and the Spanish MINECO (Grant No. MAT2013-46593-C6-01). M. C. acknowledges support from the Alexander von Humboldt Foundation.Peer Reviewe

Tunable self-assembly of one-dimensional nanostructures with orthogonal directions

High-temperature exposure of a Mo(110) surface to borazine (HBNH)3leads to the formation of two distinctly different self-assembling nanostructures. Depending on the substrate temperature during preparation, either well-aligned, ultra-thin boron nanowires or a single-layer stripe structure of hexagonal boron nitride forms. Both structures show one-dimensional (1D) characteristics, but in directions perpendicular to each other. It is also possible to grow the two phases in coexistence. The relative weights are controlled by the sample temperature during preparation

Modifying the Cu(111) Shockley surface state by Au alloying

The deposition of submonolayer amounts of Au onto Cu(111) results in a Au-Cu surface alloy with temperature- and thickness-dependent stoichiometry. Upon alloying, the characteristic Shockley state of Cu(111) is modified, shifting to 0.53 eV binding energy for a particular surface Au2Cu concentration, which is a very high binding energy for a noble-metal surface. Based on a phase accumulation model analysis, we discuss how this unusually large shift is likely reflecting an effective increase in the topmost layer thickness of the order of, but smaller than, the value expected from the moiré undulation. © 2012 American Physical Society.This work was supported in part by the Spanish MINECO (Grants No. MAT2010-21156-C03-01 and No. MAT2010-21156-C03-03), and the Basque Government (Grant No. IT-257-07). The SRC is funded by the National Science Foundation (Award No. DMR-0084402).Peer Reviewe

X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal

This work is licensed under a Creative Commons Attribution 4.0 International License.-- et al.Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Through such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. These results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions.We acknowledge financial support from the Spanish Ministry of Economy (Grants MAT2013-46593-C6-4-P and MAT2013-46593-C6-2-P ), Basque Government (Grants IT621-13 and IT756-13). A.L.W. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-SC0012704. AXBR acknowledges support from the Basque Departamento de Educación and the UPV/EHU through the Zabalduz program. AXBR, PCS and DSP acknowledge the Deutsche Forschungsgemeinschaft through the Sonderforschungsbereich 1083.Peer Reviewe

Electroluminescence of copper-nitride nanocrystals

Nanocrystals can behave as quantum boxes with confined electronic states governing their optoelectronic properties. The formation of nanometer-size crystals of copper nitride (Cu3N) grown by nitrogen sputtering of a Cu(110) surface is reported. Scanning tunneling spectroscopy shows that the nanocrystals exhibit a series of well-defined sharp electronic resonances, which correspond to confined free-electron-like states. We observe that electrons from a scanning tunneling microscope tip induce the emission of light with a larger efficiency than on the bare metal surface. The spectral analysis of the emitted photons reveals various radiative inelastic pathways enabled by the confined states, which explain the enhanced light emission. Thus, the Cu3N nanocrystals can be employed as nanometer-size light sources

Survival of spin state in magnetic porphyrins contacted by graphene nanoribbons

We report on the construction and magnetic characterization of a fully functional hybrid molecular system composed of a single magnetic porphyrin molecule bonded to graphene nanoribbons with atomically precise contacts. We use on-surface synthesis to direct the hybrid creation by combining two molecular precursors on a gold surface. High-resolution imaging with a scanning tunneling microscope finds that the porphyrin core fuses into the graphene nanoribbons through the formation of new carbon rings at chemically predefined positions. These ensure the stability of the hybrid and the extension of the conjugated character of the ribbon into the molecule. By means of inelastic tunneling spectroscopy, we prove the survival of the magnetic functionality of the contacted porphyrin. The molecular spin appears unaffected by the graphenoid electrodes, and we simply observe that the magnetic anisotropy appears modified depending on the precise structure of the contacts.We acknowledge the financial support from Spanish Agencia Estatal de Investigación (AEI) (project nos. MAT2016-78293-C6 and FIS2015-62538-ERC, and the Maria de Maeztu Units of Excellence Programme MDM-2016-0618), the Basque Government (Department Industry, grant no. PI-2015-1-42), the European project PAMS (610446), the Xunta de Galicia (Centro singular de investigación de Galicia accreditation 2016 to 2019, ED431G/09), the European Research Council (grant agreement no. 635919), and the European Regional Development FundS

Electronic Properties of Substitutionally Boron-doped Graphene Nanoribbons on a Au(111) Surface

High quality graphene nanoribbons (GNRs) grown by on-surface synthesis strategies with atomic precision can be controllably doped by inserting heteroatoms or chemical groups in the molecular precursors. Here, we study the electronic structure of armchair GNRs substitutionally doped with di-boron moieties at the center, through a combination of scanning tunneling spectroscopy, angle-resolved photoemission, and density functional theory simulations. Boron atoms appear with a small displacement towards the surface signaling their stronger interaction with the metal. We find two boron-rich flat bands emerging as impurity states inside the GNR band gap, one of them particularly broadened after its hybridization with the gold surface states. In addition, the boron atoms shift the conduction and valence bands of the pristine GNR away from the gap edge, and leave unaffected the bands above and below, which become the new frontier bands and have negligible boron character. This is due to the selective mixing of boron states with GNR bands according to their symmetry. Our results depict that the GNRs band structure can be tuned by modifying the separation between di-boron moieties.Comment: 12 pages, 5 Figure

Exploring energy performance certificates through visualization

Energy Performance Certificates (EPCs) provide interesting information on the standard-based calculation of energy performance, thermo-physical and geometrical related properties of a building. Because of the volume of available data (issued as open data) and the heterogeneity of the attributes, the exploration of these energy-related data collections is challenging. This paper presents INDICE (INformative DynamiC dashboard Engine), a new data visualization framework able to automatically explore large collections of EPCs. INDICE explores EPCs through both querying and analytics tasks, and intuitively presents the output through informative dashboards. The latter include dynamic and interactive maps along with different informative charts allowing different stakeholders (e.g., domain and non-domain expert users) to explore and interpret the extracted knowledge at different spatial granularity levels. The objective of INDICE is to create energy maps useful for the characterization of the energy performance of buildings located in different areas. The experimental evaluation, performed on a real set of EPCs related to a major Italian region in the North West of Italy, demonstrates the effectiveness of INDICE in exploring an EPC dataset through different data and knowledge visualization techniques