RESUMEN
Within the collection of surface-supported reactions currently accessible for the production of extended molecular nanostructures under ultra-high vacuum, Ullmann coupling has been the most successful in the controlled formation of covalent single C-C bonds. Particularly advanced control of this synthetic tool has been obtained by means of hierarchical reactivity, commonly achieved by the use of different halogen atoms that consequently display distinct activation temperatures. Here we report on the site-selective reactivity of certain carbon-halogen bonds. We use precursor molecules halogenated with bromine atoms at two non-equivalent carbon atoms and found that the Ullmann coupling occurs on Au(111) with a remarkable predilection for one of the positions. Experimental evidence is provided by means of scanning tunneling microscopy and core level photoemission spectroscopy, and a rationalized understanding of the observed preference is obtained from density functional theory calculations.
RESUMEN
We investigate the thermally induced cyclization of 1,2-bis(2-phenylethynyl)benzene on Au(111) using scanning tunneling microscopy and computer simulations. Cyclization of sterically hindered enediynes is known to proceed via two competing mechanisms in solution: a classic C(1)-C(6) (Bergman) or a C(1)-C(5) cyclization pathway. On Au(111), we find that the C(1)-C(5) cyclization is suppressed and that the C(1)-C(6) cyclization yields a highly strained bicyclic olefin whose surface chemistry was hitherto unknown. The C(1)-C(6) product self-assembles into discrete noncovalently bound dimers on the surface. The reaction mechanism and driving forces behind noncovalent association are discussed in light of density functional theory calculations.
RESUMEN
Activating the strong C-C σ-bond is a central problem in organic synthesis. Directly generating activated C centers by metalation of structures containing strained four-membered rings is one maneuver often employed in multistep syntheses. This usually requires high temperatures and/or precious transition metals. In this paper, we report an unprecedented C-C σ-bond activation at room temperature on Cu(111). By using bond-resolving scanning probe microscopy, we show the breaking of one of the C-C σ-bonds of a biphenylene derivative, followed by insertion of Cu from the substrate. Chemical characterization of the generated species was complemented by X-ray photoemission spectroscopy, and their reactivity was explained by density functional theory calculations. To gain further insight into this unique reactivity on other coinage metals, the reaction pathway on Ag(111) was also investigated and the results were compared with those on Cu(111). This study offers new synthetic routes that may be employed in the in situ generation of activated species for the on-surface synthesis of novel C-based nanostructures.
RESUMEN
Isoselenocyanates are valuable coupling partners required for preparing key chemical intermediates and biologically active molecules in an accelerated and effective way. Likewise, (Z)-2-oxo-N-phenylpropanehydrazonoyl chlorides have been employed in numerous one-step heteroannulation reactions to assemble the structural core of several various kinds of heterocyclic compounds. Here, we describe the inverse electron demand 1,3-dipolar cycloaddition reaction of isoselenocyanates with a variety of substituted (Z)-2-oxo-N-phenylpropanehydrazonoyl chlorides to generate, regioselectively and stereoselectively, a series of 5-arylimino-1,3,4-selenadiazole derivatives comprising a multitude of functional groups on both aryl rings. The synthetic method features gentle room-temperature conditions, wide substrate scope, and good to high reaction yields. The selenadiazoles were separated by gravity filtration in all instances and chemical structures were validated by multinuclear NMR spectroscopy and high accuracy mass spectral measurements. First conclusive molecular structure elucidation of the observed 5-arylimino-selenadiazole regioisomer was verified by single-crystal X-ray diffraction analysis. Crystal-structure measurement was successfully carried out on (Z)-1-(4-(4-iodophenyl)-5-(p-tolylimino)-4,5-dihydro-1,3,4-selenadiazol-2-yl)ethan-1-one and (Z)-1-(5-((4-methoxyphenyl)imino)-4-(4-(methylthio)phenyl)-4,5-dihydro-1,3,4-selenadiazol-2-yl)ethan-1-one. Likewise, the (Z)-geometry of the hydrazonoyl chloride reactant was proven by X-ray diffraction studies. As representative examples, crystal-structure determination was carried out on (Z)-2-oxo-N-phenylpropanehydrazonoyl chloride and (Z)-N-(3,5-bis(trifluoromethyl)phenyl)-2-oxopropanehydrazonoyl chloride. Density functional theory calculations at the B3LYP-D4/def2-TZVP level were conducted to support the noted experimental findings and suggested mechanism.
RESUMEN
The present study elucidates the factors that govern the spontaneous self-assembly of a family of dimetal [Pt(2)L(4)] (L=dithiocarboxylato ligand) complexes. Experimental data show that variables such as temperature, concentration, solvent and the nature of the ligand L have a critical effect on the reversible self-assembly of supramolecular [Pt(2)L(4)](n) entities. In solution, new UV/Vis spectroscopic features emerge at low temperatures and/or high concentrations, which are attributed to the formation of oligomeric [Pt(2)L(4)](n) species. The description of intermolecular Ptâ â â Pt interactions, the main driving force for the association, was addressed from a computational perspective. The contributions from intermolecular Ptâ â â S and Sâ â â S interactions to these supramolecular assemblies were found to be repulsive. Experimental UV/Vis data have been interpreted by means of computational spectroscopy.
RESUMEN
Scanning probe microscopy has become an essential tool to not only study pristine surfaces but also on-surface reactions and molecular self-assembly. Nonetheless, due to inherent limitations, some atoms or (parts of) molecules are either not imaged or cannot be unambiguously identified. Herein, we discuss the arrangement of two different nonplanar molecular assemblies of para-hexaphenyl-dicarbonitrile (Ph6(CN)2) on Au(111) based on a combined theoretical and experimental approach. For deposition of Ph6(CN)2 on Au(111) kept at room temperature, a rhombic nanoporous network stabilized by a combination of hydrogen bonding and antiparallel dipolar coupling is formed. Annealing at 575 K resulted in an irreversible thermal transformation into a hexagonal nanoporous network stabilized by native gold adatoms. However, the Au adatoms could neither be unequivocally identified by scanning tunneling microscopy nor by noncontact atomic force microscopy. By combining van't Hoff plots derived from our scanning probe images with our density functional theory calculations, we were able to confirm the presence of the elusive Au adatoms in the hexagonal molecular network.
RESUMEN
Intercalation of molecules into layered materials is actively researched in materials science, chemistry, and nanotechnology, holding promise for the synthesis of van der Waals heterostructures and encapsulated nanoreactors. However, the intercalation of organic molecules that exhibit physical or chemical functionality remains a key challenge to date. In this work, we present the synthesis of heterostructures consisting of porphines sandwiched between a Cu(111) substrate and an insulating hexagonal boron nitride ( h-BN) monolayer. We investigated the energetics of the intercalation, as well as the influence of the capping h-BN layer on the behavior of the intercalated molecules using scanning probe microscopy and density functional theory calculations. While the self-assembly of the molecules is altered upon intercalation, we show that the intrinsic functionalities, such as switching between different porphine tautomers, are preserved. Such insulator/molecule/metal structures provide opportunities to protect organic materials from deleterious effects of atmospheric environment, can be used to control chemical reactions through spatial confinement, and give access to layered materials based on the ample availability of synthesis protocols provided by organic chemistry.
RESUMEN
Carbon nanotubes are a natural choice as gas sensor components given their high surface to volume ratio, electronic properties, and capability to mediate chemical reactions. However, a realistic assessment of the interaction of the tube wall and the adsorption processes during gas phase reactions has always been elusive. Making use of ultraclean single-walled carbon nanotubes, we have followed the adsorption kinetics of NO2 and found a physisorption mechanism. Additionally, the adsorption reaction directly depends on the metallic character of the samples. Franck-Condon satellites, hitherto undetected in nanotube-NOx systems, were resolved in the N 1s X-ray absorption signal, revealing a weak chemisorption, which is intrinsically related to NO dimer molecules. This has allowed us to identify that an additional signal observed in the higher binding energy region of the core level C 1s photoemission signal is due to the C â O species of ketene groups formed as reaction byproducts . This has been supported by density functional theory calculations. These results pave the way toward the optimization of nanotube-based sensors with tailored sensitivity and selectivity to different species at room temperature.