The post-synthetic modification of covalent organic frameworks (COFs) via host-guest chemistry is an important method to tailor their electronic properties for applications. Due to the limited structural control in the assembly of two-dimensional surface-supported COFs, supramolecular networks are traditionally used at present for host-guest experiments on surfaces, which lack structural and thermal stability, however. Here, we present a combined scanning tunneling microscopy and density functional theory study to understand the host-guest interaction in triphenylamine-based covalently-linked macrocycles and networks on Au(111). These triphenylamine-based structures feature carbonyl and hydrogen functionalized pores that create preferred adsorption sites for trimesic acid (TMA) and halogen atoms. The binding of the TMA through optimized hydrogen-bond interactions is corroborated by selective adsorption positions within the pores. Band structure calculations reveal that the strong intermolecular charge transfer through the TMA bonding reduces the band gap in the triphenylamine COFs, demonstrating the concept of supramolecular doping by host-guest interactions in surface-supported COFs. Halogen atoms selectively adsorb between two carbonyl groups at Au hollow sites. The mainly dispersive interaction of the halogens with the triphenylamine COF leads to a small downshift of the bands. Most of the halogens change their adsorption position selectively upon annealing near the desorption temperature. In conclusion, we demonstrate evidence for supramolecular doping via post-synthetic modification and to track chemical reactions in confined space.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The syntheses of five 1D coordination polymers containing the sawhorse‐type unit [Ru2(µ‐OAc)2(CO)4] linked by various bridging N,N‐donor ligands are reported. Various π‐conjugated linkers, such as trans‐[1,2‐bis(N‐methyl)imidazol‐2‐yl]ethylene (trans‐bie), pyrazine (pyz), 4,4′‐bipyridine (4,4′‐bipy) and 1,2‐bis(4‐pyridyl)ethylene (bpe) as well as the aliphatic linker 1,4‐diazabicyclo[2.2.2]octane (DABCO), were applied in the syntheses. The formation of 1D coordination polymers was proven by crystal structure determinations of two of the polymeric materials. The geometries and electronic structures of all polymers were analysed further by CASSCF/CASPT2 and DFT calculations based on monomeric model compounds. Finally, first attempts regarding deposition of the 1D chain, the sawhorse fragment and/or the ligands on a highly ordered pyrolytic graphite surface, analysed by STM measurements, are also reported.

Based on scanning tunneling microscopy experiments combined with density functional theory, we report the formation and the electronic structure of porous binary supramolecular networks on Au(111). The two triphenylamine derivatives with identical scaffolds intermix due to a maximization of the overall number of H-bonds instead of an optimization of the H-bond strength in the bonding motif. The HOMO-LUMO gap is defined by both molecules, which is typical for electron donor-acceptor networks.

The generic structure of most high Tc superconductors is a stacking sequence of superconducting planes separated by so‐called charge reservoir layers. It is well known that carrier doping of these materials is achieved either by substitution of atoms or by nonstoichiometry in the charge reservoir layer. The alternating type of stacking causes yet another two important consequences. First, the transport anisotropy of these materials can be so high, that in the superconducting state the c‐axis transport is governed by the intrinsic Josephson effect. Whereas the anisotropy of our investigated LaO1–xFxFeAs samples was not sufficient, optimum‐doped Ca10(FeAs)10Pt4As8 showed hysteretic c‐axis current–voltage characteristics. Together with the Ambegaokar–Baratoff like temperature dependence of the critical current, this is a strong indication of intrinsic Josephson effects. Second, it is possible to deposit in the charge reservoir layers a substantial amount of charge only by injecting large c‐axis currents. By charge compensation, this decreases the concentration of mobile electrons in the conducting layers of electron‐doped materials. We were able to verify this in all details by c‐axis transport measurements of LaO1−xFxFeAs single crystals and pure and Pt doped (CaFe1–xPtxAs)10Pt4As8 single crystals. After current injection, we observed a decrease of Tc for doping levels at or below the Tc maximum, and a Tc increase for doping levels beyond the maximum. In all cases, the resistivity of the samples increased significantly. In both material classes, heavily overdoped samples showed a spectacular Tc increase by more than 10 K only accomplished by carrier injection.Generic stacking sequence of layered superconductors and crystal structure of the pnictide LaOFeAs.

The fabrication of nanostructures in a bottom-up approach from specific molecular precursors offers the opportunity to create tailored materials for applications in nanoelectronics. However, the formation of defect-free two-dimensional (2D) covalent networks remains a challenge, which makes it difficult to unveil their electronic structure. Here we report on the hierarchical on-surface synthesis of nearly defect-free 2D covalent architectures with carbonyl-functionalized pores on Au(111), which is investigated by low-temperature scanning tunnelling microscopy in combination with density functional theory calculations. The carbonyl-bridged triphenylamine precursors form six-membered macrocycles and one-dimensional (1D) chains as intermediates in an Ullmann-type coupling reaction that are subsequently interlinked to 2D networks. The electronic band gap is narrowed when going from the monomer to 1D and 2D surface-confined π -conjugated organic polymers comprising the same building block. The significant drop of the electronic gap from the monomer to the polymer confirms an efficient conjugation along the triphenylamine units within the nanostructures.

The adsorption, chemical nature, and self-assembly of diaminotriazinyl- and carboxyl-substituted triphenylamines with dimethylmethylene bridges were studied on Au(111) and Cu(111) at submonolayer coverage by low-temperature scanning tunneling microscopy and density functional theory. On Au(111), both molecules form extended porous honeycomb networks. The geometry of the networks agrees well with density functional theory optimized hydrogen-bonded gas phase structures. Therefore, the self-assemblies on Au(111) are strongly directed by intermolecular hydrogen bond interactions. In contrast, on Cu(111) both molecules aggregate in dense islands owing to the stronger moleculesurface interaction. While the carboxyl substituents partially deprotonate at room temperature on Cu(111), the diaminotriazinyl-substituted triphenylamines adsorb mainly intact. The diaminotriazinyl groups deprotonate gradually at increased adsorption temperatures.

Graphene grown on Rh(111) was used as a template for the growth of Pd nanoclusters. Using high-resolution synchrotron radiation-based X-ray photoelectron spectroscopy, we studied the deposition of Pd on corrugated graphene in situ. From the XP spectra, we deduce a cluster-by-cluster growth mode. The formation of clusters with 3 nm diameter was confirmed by low-temperature scanning tunneling microscopy measurements. The investigation of the thermal stability of the Pd particles showed three characteristic temperature regimes: Up to 550 K restructuring of the particles takes place, between 550 and 750 K the clusters coalesce into larger agglomerates, and finally between 750 and 900 K Pd intercalates between the graphene layer and the Rh surface.

Conformational changes in the conjugated backbone of poly- and oligodiacetylenes (PDAs and ODAs) play an important role in determining the electronic properties of these compounds. At the same time, conformational changes can also result in a folded structure that shows helical chirality. Using d-camphor as a chiral building block, we have designed a high-yielding, iterative synthesis of monodisperse, optically pure cis-oligodiacetylenes (ODAs). cis-ODAs up to the tridecamer have been formed, which is the longest monodisperse cis-ODA reported to date. UV/Vis spectroscopy suggests a large effective conjugation length in THF, likely the result of a linear, planar conformation in this solvent. High-resolution STM/AFM measurements of the nonamer cast from THF onto HOPG show a linear structure. In iPrOH, circular dichroism (CD) spectra suggest the formation of chiral aggregates for ODAs with at least nine d-camphor units, based on a strong CD response.

AbstractKonformationsänderungen des konjugierten Rückgrats von Poly‐ und Oligodiacetylenen (PDAs und ODAs) spielen bei der Bestimmung der elektronischen Eigenschaften dieser Verbindungen eine wichtige Rolle. Gleichzeitig können Konformationsänderungen auch zu gefalteten Strukturen führen, die helikale Chiralität aufweisen. Durch Verwendung von D‐Campher als chiraler Baustein konnten monodisperse, optisch reine cis‐Oligodiacetylene (ODAs) in hoher Ausbeute erhalten werden. cis‐ODAs bis zur Länge des Tridecamers wurden synthetisiert, was dem längsten bisher bekannten monodispersen cis‐ODA entspricht. UV/Vis‐Spektroskopie deutet auf eine hohe effektive Konjugationslänge in THF hin, vermutlich aufgrund einer linearen planaren Konformation in diesem Lösungsmittel. Hochauflösende STM/AFM‐Messungen von Filmen des Nonamers, abgeschieden aus einer THF‐Lösung auf HOPG, zeigen eine lineare Struktur. In iPrOH gemessene Zirkulardichroismus(CD)‐Spektren legen die Bildung chiraler Aggregate der ODAs mit mindestens neun D‐Campher‐Einheiten nahe. Die CD‐Resonanz ist konzentrations‐ und temperaturabhängig.