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Johannes V Barth

Publications and source records attributed to Johannes V Barth.

At least 19 recordsLinked to original sources
PubMed2007

Controlled metalation of self-assembled porphyrin nanoarrays in two dimensions.

We report a bottom-up approach for the fabrication of metallo-porphyrin compounds and nanoarchitectures in two dimensions. Scanning tunneling microscopy and tunneling spectroscopy observations elucidate the interaction of highly regular porphyrin layers self-assembled on a Ag(111) surface with iron monomers supplied by an atomic beam. The Fe is shown to be incorporated selectively in the porphyrin macrocycle whereby the template structure is strictly preserved. The immobilization of the molecular reactants allows the identification of single metalation events in a novel reaction scheme. Because the template layers provide extended arrays of reaction sites, superlattices of coordinatively unsaturated and magnetically active metal centers are obtained. This approach offers novel pathways to realize metallo-porphyrin compounds, low-dimensional metal-organic architectures and patterned surfaces which cannot be achieved by conventional means.

Metalloporphyrins↗
PubMed2006

Surface-template assembly of two-dimensional metal-organic coordination networks.

The self-assembly of iron-coordinated two-dimensional metal-organic networks on a Cu(100) surface has been investigated by scanning tunneling microscopy under ultra-high-vacuum conditions. We applied three rodlike polybenzene dicarboxylic acid molecules with different backbone lengths as organic linkers. The three linker molecules form topologically identical rectangular networks with Fe, all comprising iron pairs as the network nodes. Whereas the length of the linker molecules defines the dimension of the networks, the substrate also significantly influences the structural details, e.g., network orientation with respect to the substrate, geometric shape of the network cavities, Fe-carboxylate coordination configuration, and iron-iron distance.

Journal Article↗
PubMed2006

Asymmetry induction by cooperative intermolecular hydrogen bonds in surface-anchored layers of achiral molecules.

The mesoscale induction of two-dimensional supramolecular chirality (formation of 2D organic domains with a single handedness) was achieved by self-assembly of 1,2,4-benzenetricarboxylic (trimellitic) acid on a Cu(100) surface at elevated temperatures. The combination of spectroscopic [X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS)], real-space-probe [scanning tunneling microscopy (STM)], and computational [density functional theory (DFT)] methods allows a comprehensive characterization of the obtained organic adlayers, where details of molecular adsorption geometry, intermolecular coupling, and surface chemical bonding are elucidated. The trimellitic acid species, comprising three functional carboxylic groups, form distinct stable mirror-symmetric hydrogen-bonded domains. The chiral ordering is associated with conformational restriction in the domains: molecules anchor to the substrate with an ortho carboxylate group, providing two para carboxylic acid moieties for collective lateral interweaving through H bonding, which induces a specific tilt of the molecular plane. The ease of molecular symmetry switching in domain formation makes homochiral-signature propagation solely limited by the terrace width. The molecular layer modifies the morphology of the underlying copper substrate and induces mum-sized strictly homochiral terraces.

Journal Article↗
PubMed2006

Density functional theory analysis of carboxylate-bridged diiron units in two-dimensional metal-organic grids.

Carboxylate-bridged diiron units have been realized recently in two dimensions via metal-directed self-assembly of simple organic linkers. They represent notably a coupling motif stabilizing a series of nanoporous metal-organic coordination networks and are reminiscent of catalytically active sites in metalloproteins. To rationalize their atomic structure, chemical bonding, and electronic properties, we performed density functional theory calculations for exemplary Fe-terephthalate grids assembled on the Cu(100) surface. The obtained atomistic description and understanding is decisive for the considerate use of two-dimensional metal-organic coordination networks as templates, guest systems, or catalysts.

Journal Article↗
PubMed2006

Monitoring two-dimensional coordination reactions: directed assembly of co-terephthalate nanosystems on Au(111).

We report scanning tunneling microscopy observations on the formation of 2D Co-based coordination compounds on the reconstructed Au(111) surface. Preorganized arrays of Co bilayer islands are shown to be local reaction sites, which are consumed in the formation of Co-terephthalate aggregates and regular nanoporous grids. The latter exhibit a planar geometry stabilized by the smooth substrate. The nanogrids are based on a rectangular motif, which is understood as an intrinsic feature of a 2D cobaltous terephthalate sheet and dominates over the templating influence of the quasihexagonal substrate atomic lattice. The dynamics of the Co island dissolution and metallosupramolecular self-assembly could be monitored in situ. Complementary first-principles calculations were performed to analyze the underlying driving forces and to examine general trends in 2D metal-carboxylate formation. The findings indicate the wide applicability of coordination chemistry concepts at surfaces, which moreover can be spatially confined by using templated substrates, and its potential to synthesize arrangements unavailable in bulk materials.

Journal Article↗
PubMed2005

Enhanced field emission from multiwall carbon nanotube films by secondary growth.

We have studied nickel, gold, and ferritin coatings on catalytically grown multiwall carbon nanotubes as well as the generation of secondary nanotubes by resubmitting the decorated nanotubes to the chemical vapor deposition process. Nickel layers sputtered on nanotubes show a stronger interaction with the nanotube walls than gold coatings. At ambient temperature this results in a metal film that is more homogeneous for Ni than for Au. Surface mass transport at elevated temperatures leads to a transformation of the coating to nanoscale clusters on the nanotube surface. The resulting Au clusters are spherelike with a very small contact area with the nanotube whereas the Ni clusters are stretched along the tube axis and have a large contact area. Secondary nanotubes were established by growing nanotubes directly on the walls of primary nanotubes. Thin Ni layers or ferritin served as catalysts. We compared the field emission properties of samples with and without secondary nanotubes. The presence of secondary nanotubes enhances the field emission substantially.

Journal Article↗
PubMed2005

Engineering atomic and molecular nanostructures at surfaces.

The fabrication methods of the microelectronics industry have been refined to produce ever smaller devices, but will soon reach their fundamental limits. A promising alternative route to even smaller functional systems with nanometre dimensions is the autonomous ordering and assembly of atoms and molecules on atomically well-defined surfaces. This approach combines ease of fabrication with exquisite control over the shape, composition and mesoscale organization of the surface structures formed. Once the mechanisms controlling the self-ordering phenomena are fully understood, the self-assembly and growth processes can be steered to create a wide range of surface nanostructures from metallic, semiconducting and molecular materials.

Journal Article↗
PubMed2005

Chiral phase transition in two-dimensional supramolecular assemblies of prochiral molecules.

The self-assembly of the rodlike two-dimensional chiral molecule 4-[trans-2-(pyrid-4-yl-vinyl)] benzoic acid on the Cu(100) surface has been investigated by scanning tunneling microscopy. Upon adsorption at T>or=300 K, the molecules are deprotonated and assemble in parquet patterns when the coverage remains below a critical value. Corresponding high-resolution data reveal that the ordering implies mesoscopic chiral resolution as a result of chiroselective interactions (i.e., two domains comprise exclusively one enantiomer). When the critical coverage is exceeded, an abrupt transition to a single racemic phase is observed with a different lateral molecular coupling scheme. The shifting of the subtle balance between the weak lateral coupling, substrate bonding, and the packing requirements encountered with the increased molecular coverage is suggested to be the driving force for this homochiral-to-heterochiral phase transition.

Journal Article↗
PubMed2005

Manipulating 2D metal-organic networks via ligand control.

High-resolution scanning tunneling microscopy has revealed how ligand control can be successfully employed to eliminate isomeric phases and defects in 2D coordination networks that are self-assembled at a surface support by replacing symmetric dicarboxylato linker ligands to dissymmetric carboxylpyridyl linker ligands.

Journal Article↗
PubMed2005

Programming supramolecular assembly and chirality in two-dimensional dicarboxylate networks on a Cu(100) surface.

We report a comparative study on the 2D self-assembly of two related ditopic benzoic acid species, which have similar shape and endgroups but different backbone symmetry. High-resolution scanning tunneling microscopy data reveal how the symmetry information of molecular building blocks is readily expressed in the resulting chiral or nonchiral supramolecular networks. The underlying square Cu(100) surface steers network orientation and accounts for carboxylate formation, resulting in an unusual intermolecular hydrogen bond motif. Our results demonstrate that symmetry and chiral resolution in 2D supramolecular assembly can be controlled via the design of functional molecules and choice of substrate.

Adsorption↗
PubMed2004

Design of extended surface-supported chiral metal-organic arrays comprising mononuclear iron centers.

A design strategy for fabricating a surface-supported chiral metal-organic system comprising a regular arrangement of mononuclear iron centers and nanocavities is presented. By sequential deposition of 1,2,4-benzenetricarboxylic acid (tmla) molecules and iron atoms on a Cu(100) surface under ultrahigh vacuum conditions, chiral square-planar Fe(tmla)4 metal-organic complexes are generated, which order in extended homochiral arrays. Structure formation and envisioned functionality of such metal-organic architectures are discussed.

Benzene Derivatives↗
PubMed2004

Towards surface-supported supramolecular architectures: tailored coordination assembly of 1,4-benzenedicarboxylate and Fe on Cu(100).

We present a comprehensive investigation of the modular assembly of surface-supported metal-organic coordination systems with specific topologies and high structural stability formed by vapor deposition of 1,4-benzenedicarboxylic acid molecules and iron atoms on a Cu(100) surface under ultra-high vacuum conditions. By making use of the two carboxylate moieties available for lateral linkage to Fe atoms, we succeeded in the fabrication of distinct Fe-carboxylate coordination architectures at the surface by carefully adjusting the ligand and metal concentration ratio and the temperature of the post-deposition annealing treatment. The mononuclear, 1D-polymeric and fully 2D-reticulated metallosupramolecular arrangements obtained were characterized in situ at the single-molecule level by scanning tunneling microscopy.

Journal Article↗
PubMed2004

Steering molecular organization and host-guest interactions using two-dimensional nanoporous coordination systems.

Metal-organic coordination networks (MOCNs) have attracted wide interest because they provide a novel route towards porous materials that may find applications in molecular recognition, catalysis, gas storage and separation. The so-called rational design principle-synthesis of materials with predictable structures and properties-has been explored using appropriate organic molecular linkers connecting to metal nodes to control pore size and functionality of open coordination networks. Here we demonstrate the fabrication of surface-supported MOCNs comprising tailored pore sizes and chemical functionality by the modular assembly of polytopic organic carboxylate linker molecules and iron atoms on a Cu(100) surface under ultra-high-vacuum conditions. These arrays provide versatile templates for the handling and organization of functional species at the nanoscale, as is demonstrated by their use to accommodate C(60) guest molecules. Temperature-controlled studies reveal, at the single-molecule level, how pore size and chemical functionality determine the host-guest interactions.

Adsorption↗
PubMed2003

Hierarchical assembly of two-dimensional homochiral nanocavity arrays.

We demonstrate the rational design of nanoporous two-dimensional supramolecular structures by the hierarchical assembly of organic molecules and transition metal atoms at surfaces. Single-molecule level observations with scanning tunneling microscopy monitor the successive aufbau of structures with increasing complexity. From the primary components secondary mononuclear chiral complexes are formed, which represent antecedents for tertiary polynuclear metal-organic nanogrids. These nanogrids represent the constituents of the eventually evolving two-dimensional networks comprising homochiral nanocavity arrays. Our findings visualize the evolution of complex matter in an exemplary way: from per se achiral species via chiral intermediates to mesoscale dissymmetric structures.

Journal Article↗