Pyrid-4-yl-vinyl)] Benzoic Acid Research Articles

Binding Geometry of Hydrogen-Bonded Chain Motif in Self-Assembled Gratings and Layers on Ag(111)

Upon adsorption on the (111) facet of Ag, 4-[trans-2-(pyrid-4-yl-vinyl)] benzoic acid (PVBA) self-assembles into a highly ordered, chiral twin chain structure at submonolayer coverages with domains that can extend for micrometers in one dimension. Using polarization-dependent measurements of C and N K-shell excitations in near-edge X-ray absorption fine structure (NEXAFS) spectra, we determine the binding geometry of single PVBA molecules within this unique ensemble for both low and high coverage regimes. At submonolayer coverage, the molecule is twisted to facilitate the formation of hydrogen bonds. The gas-phase planarity is gradually recovered as the coverage is increased, with complete planarity coinciding with loss of order in the overlayer. Thermal treatment of the PVBA film results in deprotonation of the carboxyl tail of the molecule, but despite the suppression of the stabilizing hydrogen-bonds, the overlayer remains ordered.

Self-Assembled Trimer Structures Highlight the Competitive Roles of Intermolecular and Adsorbate–Substrate Interactions: PVBA Trimer on Pd(111)

We observed the orientation of 4-trans-2-(pyrid-4-yl-vinyl)benzoic acid (PVBA) trimers on Pd(111) using scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV). The image showed three different types of trimers, one of which does not follow predicted dimer orientations. This type of trimer displays 10° rotations of each molecule in clockwise or counterclockwise directions. Calculations of adsorbate-substrate energy and hydrogen bonding energy revealed that the rotations are a result of competition between adsorbate-adsorbate and adsorbate-substrate interactions.

Influence of Subsurface Layers on the Adsorption of Large Organic Molecules on Close-Packed Metal Surfaces

The asymmetric molecule 4-[trans-2-(pyrid-4-yl-vinyl)] benzoic acid (PVBA) adsorbed on Cu(111) is characterized by scanning tunneling microscopy (STM) and density functional theory (DFT) to determine the influence of subsurface atomic layers on the adsorption. In contrast to the 6-fold symmetry of the first atomic layer of close-packed surfaces, we find that the arrangement of the isolated molecules follows predominantly a 3-fold symmetry. This reduction in symmetry, where the molecule selects a specific orientation along the ⟨-211⟩ axes, reveals the contribution of lower-lying Cu layers to the molecular arrangement. Our calculations rationalize the interaction of the substrate with the molecule in terms of electrostatic screening and local relaxation phenomena.

Chiral Recognition of PVBA on Pd(111) and Ag(111) Surfaces

An asymmetric planar molecule, 4-trans-2-(pyrid-4-yl-vinyl) benzoic acid (PVBA), has been used to establish the organic chiral recognition on fcc(111) metal surfaces. The strong correlation between the orientation and chiral recognition of PVBA on both Ag(111) and Pd(111) guides the choice of a model potential, which determines the relative binding energy of PVBA on fcc(111). An angle-dependent calculation of relative binding energy reproduces the experimental observation of the chiral recognition of PVBA on Ag(111) but not on Pd(111).

Mesoscopic chiral reshaping of the Ag(110) surface induced by the organic molecule PVBA.

We report scanning tunneling microscopy observations on the restructuring of a Ag(110) surface induced by the molecule 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA). Our data reveal that the surface undergoes a mesoscopic step faceting following exposure to submonolayer coverages and thermal activation. A sawtooth arrangement evolves implying long-range mass transport of substrate atoms and forming a regular arrangement of kink sites. Its formation is associated with the molecules' functional headgroups forming carboxylates with [100] Ag microfacets at step edges, and eventually operating to reshape the surface morphology. Interestingly, the resulting microfacets act as chiral templates for the growth of supramolecular PVBA structures. Theoretical modeling based on ab initio results indicates that chiral recognition processes discriminating between the two enantiomers of adsorbed PVBA molecules occur in this process.

Adsorption-induced chirality influences surface orientation in organic self-assembled structures: an STM study of PVBA on Pd(1 1 1)

The adsorption of the planar organic molecule, 4- trans-2-(pyrid-4-yl-vinyl) benzoic acid (PVBA), on Pd(1 1 1) under ultrahigh vacuum conditions produces molecular dimers and trimers. Scanning tunneling microscopy (STM) images reveal that dimers are formed preferentially over the trimer structures. Adsorption of the asymmetric planar molecule induces chirality in the adsorbed structures and results in homo-chiral and hetero-chiral dimers of PVBA. The STM results further reveal an orientation-specific adsorption of the different chiralities. A statistical analysis of the observed structures indicates an equivalent presence of the two dimer types on a surface not inherently offering any form of chiral recognition. The chiral dimer pairs are further resolved through site-specific adsorption orientations with respect to the Pd lattice. These investigations demonstrate the cooperative roles of substrate–adsorbate binding and intermolecular interactions in the formation of these self-assembled structures.

Supramolecular architectures and nanostructures at metal surfaces

The controlled formation of non-covalent bonds (H-bonding, metal–ligand interactions) is the key ingredient for the fabrication of supramolecular architectures and nanostructures. Upon deposition of molecular building blocks at well-defined surfaces, this issue can be directly addressed. Scanning tunneling microscopy observations are presented, which provide insight into the interaction of functional groups on metal substrates at the molecular level. In particular, carboxylic acids were employed: (4-[(pyrid-4-yl-ethynyl)]-benzoic acid (PEBA), 4-[trans-2-(pyrid-4-yl-vinyl)]-benzoic acid (PVBA) and trimesic acid (1,3,5-benzenetricarboxylic acid, TMA), which could be stabilized in a flat geometry at the surface. By choosing the appropriate substrate material and symmetry, the sensitive balance of intermolecular and molecule–substrate interactions can be tuned to obtain well-defined supramolecular architectures and nanostructures. The head-to-tail hydrogen bonding of the related rod-like species PEBA and PVBA stabilizes molecular rows on Ag(111). The subtle difference in the molecular geometries is reflected in the lateral ordering: While 2-D islanding is encountered with PEBA, 1-D nanogratings of supramolecular chiral H-bonded twin chains evolve for PVBA. The threefold symmetry of TMA in conjunction with the self-complementarity of its exodentate groups accounts for the formation of H-bonded honeycomb networks on Cu(100) at low temperatures. Metal–ligand interactions were probed with PVBA and TMA at Cu surfaces at ambient temperature. Deprotonation of the carboxyl moiety takes place, which readily interacts with Cu adatoms evaporated from step edges. This leads to a head-to-head pairing of PVBA on Cu(111) and cloverleaf-shaped Cu–TMA coordination compounds on Cu(001).

Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA on Ag(111).

We present investigations on noncovalent bonding and supramolecular self-assembly of two related molecular building blocks at a noble metal surface: 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA) and 4-[(pyrid-4-yl-ethynyl)]benzoic acid (PEBA). These rigid, rodlike molecules comprising the same complementary moieties for hydrogen bond formation are comparable in shape and size. For PVBA, the ethenylene moiety accounts for two-dimensional (2-D) chirality upon confinement to a surface; PEBA is linear and thus 2-D achiral. Molecular films were deposited on a Ag(111) surface by organic molecular beam epitaxy and characterized by scanning tunneling microscopy. At low temperatures (around 150 K), both species form irregular networks of flat lying molecules linked via their endgroups in a diffusion-limited aggregation process. In the absence of kinetic limitations (adsorption or annealing at room temperature), hydrogen-bonded supramolecular assemblies form which are markedly different. With PVBA, enantiomorphic twin chains in two mirror-symmetric species running along a high-symmetry direction of the substrate lattice form by diastereoselective self-assembly of one enantiomer. The chirality signature is strictly correlated between neighboring twin chains. Enantiopure one-dimensional (1-D) supramolecular nanogratings with tunable periodicity evolve at intermediate coverages, reflecting chiral resolution in micrometer domains. In contrast, PEBA assembles in 2-D hydrogen-bonded islands, which are enantiomorphic because of the orientation of the supramolecular arrangements along low-symmetry directions of the substrate. Thus, for PVBA, chiral molecules form 1-D enantiomorphic supramolecular structures because of mesoscopic resolution of a 2-D chiral species, whereas with PEBA, the packing of an achiral species causes 2-D enantiomorphic arrangements. Model simulations of supramolecular ordering provide a deeper understanding of the stability of these systems.

Binding and ordering of large organic molecules on an anisotropic metal surface: PVBA on Pd(110)

The adsorption and ordering characteristics of 4- trans-2-(pyrid-4-yl-vinyl) benzoic acid (PVBA) on a Pd(110) surface were investigated by variable temperature scanning tunneling microscopy. PVBA is a rigid organic molecule ( m=225 amu) designed for nonlinear optics. The molecules adsorb flat on the surface and bind diagonally to three neighbouring Pd-rows, which configuration is maintained at all submonolayer coverages. With the completion of the first monolayer a parquet pattern evolves, resulting from the fixed bonding geometry and space limitations. Monte Carlo simulations of the film growth confirm that the monolayer ordering is stochastic in nature, even if an extrinsic precursor mechanism is operative in the adsorption. The lateral interactions between adsorbed molecules and Pd steps or adatoms at the surface are weak.

Direct observation of surface diffusion of large organic molecules at metal surfaces: PVBA on Pd(110)

The bonding and surface diffusion of 4-trans-2-(pyrid-4-yl-vinyl) benzoic acid (PVBA) on Pd(110) was investigated by variable temperature scanning tunneling microscopy at sample temperatures between 300 and 450 K. PVBA is a large organic molecule designed for nonlinear optics applications. At low coverages single PVBA molecules are randomly distributed at the surface where they bind diagonally to three neighboring Pd-rows, leading to four equivalent adsorption configurations. The “dog-bone” molecular structure could be resolved. The molecules’ surface diffusion is strictly one-dimensional along the close-packed [11̄0]-direction of the surface Pd atomic rows and obeys an Arrhenius law with an activation barrier of 0.83±0.03 eV and an attempt frequency of 1010.3±0.4 s−1.