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.

The engineering of complex architectures from functional molecules on surfaces provides new pathways to control matter at the nanoscale. In this article, we present a combined study addressing the self-assembly of the amino acid L-methionine on Ag(111). Scanning tunneling microscopy data reveal spontaneous ordering in extended molecular chains oriented along high-symmetry substrate directions. At intermediate coverages, regular biomolecular gratings evolve whose periodicity can be tuned at the nanometer scale by varying the methionine surface concentration. Their characteristics and stability were confirmed by helium atomic scattering. X-ray photoemission spectroscopy and high-resolution scanning tunneling microscopy data reveal that the L-methionine chaining is mediated by zwitterionic coupling, accounting for both lateral links and molecular dimerization. This methionine molecular recognition scheme is reminiscent of sheet structures in amino acid crystals and was corroborated by molecular mechanics calculations. Our findings suggest that zwitterionic assembly of amino acids represents a general construction motif to achieve biomolecular nanoarchitectures on surfaces.nanochemistry ͉ scanning tunneling microscopy ͉ supramolecular engineering ͉ surface chemistry ͉ x-ray photoemission spectroscopy T he controlled self-assembly of functional molecular species on well defined surfaces is a promising approach toward the design of nanoscale architectures (1). By using this methodology, regular low-dimensional systems such as supramolecular clusters, chains, or nanoporous arrays can be fabricated (2-6). A wide variety of molecular species as well as substrate materials proved to be useful (7), exploiting noncovalent directional interactions including dipole-dipole coupling (2, 3), hydrogen bridges (4,5,(8)(9)(10)(11), and metal-ligand interactions (6,(12)(13)(14)(15). With the exception of multiple H-bonded networks or coordination networks incorporating metal centers, it remains challenging to realize robust systems, and there is a need to develop protocols exploiting stronger intermolecular bonds to realize purely organic low-dimensional architectures. Small biological molecules such as amino acids or DNA base molecules represent an important class of building blocks that are of interest for molecular architectonic on surfaces because they inherently qualify for molecular recognition and self-assembly (16)(17)(18)(19)(20). The interaction between biomolecules and solid surfaces is decisive for the development of bioanalytical devices or biocompatible materials (21-23) as well as for a fundamental understanding of protein-surface bonding (24). Moreover, in three dimensions the amino acids provide assets to engineer distinct network structures based on zwitterionic coupling schemes (25-27), which may be categorized as subclass of ionic self-assembly (28), and thus are promising units to create robust nanoarchitectures. However, to date, the advantages of zwitterionic supramolecular synthons have not been exploited in ...

We present a low-temperature scanning tunneling microscopy (STM) study on the supramolecular ordering of tetrapyridyl-porphyrin (TPyP) molecules on Ag(111). Vapor deposition in a wide substrate temperature range reveals that TPyP molecules easily diffuse and self-assemble into large, highly ordered chiral domains. We identify two mirror-symmetric unit cells, each containing two differently oriented molecules. From an analysis of the respective arrangement it is concluded that lateral intermolecular interactions control the packing of the layer, while its orientation is induced by the coupling to the substrate. This finding is corroborated by molecular mechanics calculations. High-resolution STM images recorded at 15 K allow a direct identification of intramolecular features. This makes it possible to determine the molecular conformation of TPyP on Ag(111). The pyridyl groups are alternately rotated out of the porphyrin plane by an angle of 60 degrees.

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We present a combined low-temperature scanning tunneling microscopy and near-edge X-ray adsorption fine structure study on the interaction of tetrapyridyl-porphyrin (TPyP) molecules with a Cu(111) surface. A novel approach using data from complementary experimental techniques and charge density calculations allows us to determine the adsorption geometry of TPyP on Cu(111). The molecules are centered on "bridge" sites of the substrate lattice and exhibit a strong deformation involving a saddle-shaped macrocycle distortion as well as considerable rotation and tilting of the meso-substituents. We propose a bonding mechanism based on the pyridyl-surface interaction, which mediates the molecular deformation upon adsorption. Accordingly, a functionalization by pyridyl groups opens up pathways to control the anchoring of large organic molecules on metal surfaces and tune their conformational state. Furthermore, we demonstrate that the affinity of the terminal groups for metal centers permits the selective capture of individual iron atoms at low temperature.

We report a scanning tunneling microscopy study of the amino acid l-methionine on highly ordered pyrolytic graphite deposited under ambient conditions. Our experiments demonstrate the ability of l-methionine to form highly regular structures on the surface of the graphite template. By means of self-assembly, the amino acid arranges itself into an array of molecular wires, i.e., well-ordered stripes of uniform width and separation. The spacing of these wires can be controlled with the deposition amount of the amino acid, whereas the width stays constant. The width of the wires is determined by two methionine molecules arranged with their carboxyl group facing each other. The regular separation of individual wires suggest a long-range interaction among them. Molecular mechanics calculations are used to compare the experimental results with a basic model for the methionine configuration on the surface. A model for the adsorption geometry of methionine on graphite is presented.

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We have investigated the structure and morphology of the tenfold surface of decagonal Al 71.8 Ni 14.8 Co 13.4 by highly surface sensitive He atom scattering (HAS), high resolution low energy electron diffraction (SPA-LEED), and low temperature scanning tunneling microscopy (STM). The SPA-LEED patterns reveal more than 500 individual diffraction spots in the k-vector range of ͉k ʈ ͉ Ͻ 3 Å −1 . The positions of all observed diffraction spots agree with the surface projections of the reciprocal lattice structure of the type-I bulk phase. HAS shows identical spot positions as SPA-LEED, thus demonstrating a top surface layer with long range quasicrystalline order and a reciprocal lattice structure consistent with that of a bulk truncated surface. SPA-LEED peak widths are found to vary between different diffraction orders. Based on an analysis of a randomized Fibonacci sequence, this is linked to the random nature of the tiling of the type-I structure. STM measurements reveal a surface morphology characterized by rough single-height steps separating terraces with widths on the order of 100 Å. Two different surface terminations are observed, a coarse and a fine one, frequently coexisting on single terraces. The fine structure termination directly reflects the atomic structure of a bulk truncated surface, allowing a random rhombic tiling to be identified. In order to compare diffraction, real-space data, and atomic structure models, the Patterson function and autocorrelation of the surface structure, respectively, are studied. This allows an understanding of the coarse structure termination as consisting of subunits of a few atoms each arranged statistically on sites defined by the atomic tiling of the bulk tenfold planes.