Surface-mediated assembly, polymerization and degradation of thiophene-based monomers.

Ullmann coupling of halogenated aromatics is widely used in on-surface synthesis of two-dimensional (2D) polymers and graphene nanoribbons. It stands out among other reactions for regioselectively connecting aromatic monomers into 1D and 2D π-conjugated polymers, whose final structure and properties are determined by the initial building blocks. Thanks to their exceptional electronic properties, thiophene-containing monomers are frequently used for the synthesis of various conjugated materials. On the other hand, their use in on-surface polymerization is hampered by the possibility of ring opening when adsorbed on metal surfaces. In the present work, we mapped the temperature regime for these two competing reactions by investigating the adsorption of a thiophene-based prochiral molecule using scanning tunneling microscopy, X-ray photoelectron spectroscopy and density functional theory calculations. We followed the formation of organometallic (OM) networks, their evolution into covalent structures and the competition between C-C coupling and thiophene ring opening. The effect of surface reactivity was explored by comparing the adsorption on three (111) coinage metal substrates, namely Au, Ag and Cu. While outlining strategies to minimize the ring opening reaction, we found that the surface temperature during deposition is of paramount importance for the preparation of 2D OM networks, greatly enhancing the overall ordering of the product by depositing on hot Ag surface. Notably, the same protocol permits the creation of OM structures on the air-stable Au surface, thereby allowing the synthesis and application of 2D OM networks outside the ultra-high vacuum environment.

2D Supramolecular networks of dibenzonitrilediacetylene on Ag(111) stabilized by intermolecular hydrogen bonding.

The two-dimensional (2D) surface-directed self-assembly of dibenzonitrile diacetylene (DBDA) on Ag(111) under ultrahigh vacuum (UHV) conditions was investigated by combining scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and theoretical simulations based on density functional theory (DFT) calculations. The molecule consists of two benzonitrile groups (-C6H4-C[triple bond, length as m-dash]N) on each side of a diacetylene (-C[triple bond, length as m-dash]C-C[triple bond, length as m-dash]C-) backbone. The terminating nitrile (-C[triple bond, length as m-dash]N) groups at the meta position of the phenyl rings lead to cis and trans stereoisomers. The trans isomer is prochiral and can adsorb in the R or S configuration, leading to the formation of enantiomeric self-assembled networks on the surface. We identify two simultaneously present supramolecular networks, termed parallel and chevron phases, as well as a less frequently observed butterfly phase. These networks are formed from pure R (or S) domains, racemic mixtures (RS), and cis isomers, respectively. Our complementary data illustrates that the formation of the 2D supramolecular networks is driven by intermolecular hydrogen bonding between nitrile and phenyl groups (-C[triple bond, length as m-dash]NH-C6H3). This study illustrates that the molecular arrangement of each network depends on the geometry of the isomers. The orientation of the nitrile group controls the formation of the most energetically stable network via intermolecular hydrogen bonding.

Substrate Effects in the Supramolecular Assembly of 1,3,5-Benzene Tricarboxylic Acid on Graphite and Graphene.

The behavior of small molecules on a surface depends critically on both molecule-substrate and intermolecular interactions. We present here a detailed comparative investigation of 1,3,5-benzene tricarboxylic acid (trimesic acid, TMA) on two different surfaces: highly oriented pyrolytic graphite (HOPG) and single-layer graphene (SLG) grown on a polycrystalline Cu foil. On the basis of high-resolution scanning tunnelling microscopy (STM) images, we show that the epitaxy matrix for the hexagonal TMA chicken wire phase is identical on these two surfaces, and, using density functional theory (DFT) with a non-local van der Waals correlation contribution, we identify the most energetically favorable adsorption geometries. Simulated STM images based on these calculations suggest that the TMA lattice can stably adsorb on sites other than those identified to maximize binding interactions with the substrate. This is consistent with our net energy calculations that suggest that intermolecular interactions (TMA-TMA dimer bonding) are dominant over TMA-substrate interactions in stabilizing the system. STM images demonstrate the robustness of the TMA films on SLG, where the molecular network extends across the variable topography of the SLG substrates and remains intact after rinsing and drying the films. These results help to elucidate molecular behavior on SLG and suggest significant similarities between adsorption on HOPG and SLG.

Pentacene on Ni(111): room-temperature molecular packing and temperature-activated conversion to graphene.

We investigate, using scanning tunnelling microscopy, the adsorption of pentacene on Ni(111) at room temperature and the behaviour of these monolayer films with annealing up to 700 °C. We observe the conversion of pentacene into graphene, which begins from as low as 220 °C with the coalescence of pentacene molecules into large planar aggregates. Then, by annealing at 350 °C for 20 minutes, these aggregates expand into irregular domains of graphene tens of nanometers in size. On surfaces where graphene and nickel carbide coexist, pentacene shows preferential adsorption on the nickel carbide phase. The same pentacene to graphene transformation was also achieved on Cu(111), but at a higher activation temperature, producing large graphene domains that exhibit a range of moiré superlattice periodicities.

Reduced graphene oxide growth on 316L stainless steel for medical applications.

We report a new method for the growth of reduced graphene oxide (rGO) on the 316L alloy of stainless steel (SS) and its relevance for biomedical applications. We demonstrate that electrochemical etching increases the concentration of metallic species on the surface and enables the growth of rGO. This result is supported through a combination of Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM), density functional theory (DFT) calculations and static water contact angle measurements. Raman spectroscopy identifies the G and D bands for oxidized species of graphene at 1595 cm(-1) and 1350 cm(-1), respectively, and gives an ID/IG ratio of 1.2, indicating a moderate degree of oxidation. XPS shows -OH and -COOH groups in the rGO stoichiometry and static contact angle measurements confirm the wettability of rGO. SEM and AFM measurements were performed on different substrates before and after coronene treatment to confirm rGO growth. Cell viability studies reveal that these rGO coatings do not have toxic effects on mammalian cells, making this material suitable for biomedical and biotechnological applications.

Tip-induced C-H activation and oligomerization of thienoanthracenes.

The tip of a scanning tunneling microscope (STM) can be used to dehydrogenate freely-diffusing tetrathienoanthracene (TTA) molecules on Cu(111), trapping the molecules into metal-coordinated oligomeric structures. The process proceeds at bias voltages above ~3 V and produces organometallic structures identical to those resulting from the thermally-activated cross-coupling of a halogenated analogue. The process appears to be substrate dependent: no oligomerization was observed on Ag(111) or HOPG. This approach demonstrates the possibility of controlled synthesis and nanoscale patterning of 2D oligomer structures on selected surfaces.

Thermal evolution of the submonolayer near-surface alloy of ZnPd on Pd(111).

We have performed a high-resolution synchrotron radiation photoelectron spectroscopy study of the initial growth stages of the ZnPd near-surface alloy on Pd(111), complemented by scanning tunnelling microscopy data. We show that the chemical environment for surfaces containing less than half of one monolayer of Zn is chemically distinct from subsequent layers. Surfaces where the deposition is performed at room temperature contain ZnPd islands surrounded by a substrate with dilute Zn substitutions. Annealing these surfaces drives the Zn towards the substrate top-layer, and favours the completion of the first 1 : 1 monolayer before the onset of growth in the next layer.

Surface structure of Pd(111) with less than half a monolayer of Zn.

We have characterized the structural properties of submonolayer amounts of Zn on Pd(111) using scanning tunneling microscopy (STM) and spot-profile analysis low energy electron diffraction (SPA-LEED). Following room temperature deposition of ≈0.06 monolayers (ML) Zn onto Pd(111), we observe the substitution of Zn for Pd in the surface layer. At ≈0.20 ML of deposited Zn, STM reveals a locally ordered phase with a (2/√3 × 2/√3)R30° unit cell located near Zn substitutions; SPA-LEED patterns reveal the same periodicity. We attribute this phase to the metastable bonding of atoms or clusters predominantly in hollow sites surrounding Zn substitutions in the surface layer. At ≈0.4 ML, STM images reveal local (√3 × âˆš3)R30° and (2 × 1) ordering on surfaces annealed to 350 K. At coverages near 0.5 ML, both STM and SPA-LEED show the onset of the formation of the (2 × 1) ordering associated with the Zn : Pd 1 : 1 alloy phase. At all coverages, the surface is dominated by island growth; the islands' size and density is shown to depend critically on annealing at temperatures as low as 350 K. These results provide insight into the structural features of a Zn/Pd(111) coverage regime that has been much debated in recent years.

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.

Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction.

One of the great challenges in surface chemistry is to assemble aromatic building blocks into ordered structures that are mechanically robust and electronically interlinked--i.e., are held together by covalent bonds. We demonstrate the surface-confined growth of ordered arrays of poly(3,4-ethylenedioxythiophene) (PEDOT) chains, by using the substrate (the 110 facet of copper) simultaneously as template and catalyst for polymerization. Copper acts as promoter for the Ullmann coupling reaction, whereas the inherent anisotropy of the fcc 110 facet confines growth to a single dimension. High resolution scanning tunneling microscopy performed under ultrahigh vacuum conditions allows us to simultaneously image PEDOT oligomers and the copper lattice with atomic resolution. Density functional theory calculations confirm an unexpected adsorption geometry of the PEDOT oligomers, which stand on the sulfur atom of the thiophene ring rather than lying flat. This polymerization approach can be extended to many other halogen-terminated molecules to produce epitaxially aligned conjugated polymers. Such systems might be of central importance to develop future electronic and optoelectronic devices with high quality active materials, besides representing model systems for basic science investigations.

Synthesis of polyphenylene molecular wires by surface-confined polymerization.

The surface-mediated synthesis of epitaxially aligned and separated polyphenylene lines on Cu(110) by exploiting the Ullmann dehalogenation reaction is reported. Scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) show that the C-I bonds of 1,4-diiodobenzene and 1,3-diiodobenzene (C(6)H(4)I(2)) are catalytically cleaved when dosed onto the surface. Subsequent annealing transforms the copper-bound phenylene intermediates into covalent conjugated structures: linear chains of poly(p-phenylene) for 1,4-diiodobenzene and zigzag chains of poly(m-phenylene) as well as macrocyclic oligomers in the case of 1,3-diiodobenzene. The chains are strongly bound to the surface (likely through C--Cu bonds at the chain-ends) while the macrocycles are very mobile and can only be imaged by STM at low temperature. The detached halogens adsorb on the surface and separate the polymer chains from each other.

Self-assembly of rubrene on Cu(111).

We performed an ultra-high vacuum scanning tunneling microscopy (STM) investigation of the self-assembly of rubrene at room temperature on Cu(111), a metal surface with threefold symmetry. Rubrene self-assembles into two different structures called row and trimer. Both are different than the structures already observed on Cu(110) and Cu(100). Row and trimer structures have comparable molecular packing densities and are equally distributed across the surface. In the row structure the molecules are oriented with their backbone along the same high symmetry directions of the surface: [[Formula: see text]], [[Formula: see text]] or [[Formula: see text]]. The trimer structure is composed of units of three rubrene molecules, oriented along the high symmetry surface directions. These units are chiral, as revealed by height profile measurements by STM, and self-assemble in domains containing only one type of enantiomer.