André Gourdon

Properties of large organic molecules on metal surfaces

Abstract The adsorption of large organic molecules on surfaces has recently been the subject of intensive investigation, both because of the molecules’ intrinsic physical and chemical properties, and for prospective applications in the emerging field of nanotechnology. Certain complex molecules are considered good candidates as basic building blocks for molecular electronics and nanomechanical devices. In general, molecular ordering on a surface is controlled by a delicate balance between intermolecular forces and molecule–substrate interactions. Under certain conditions, these interactions can be controlled to some extent, and sometimes even tuned by the appropriate choice of substrate material and symmetry. Several studies have indicated that, upon molecular adsorption, surfaces do not always behave as static templates, but may rearrange dramatically to accommodate different molecular species. In this context, it has been demonstrated that the scanning tunnelling microscope (STM) is a very powerful tool for exploring the atomic-scale realm of surfaces, and for investigating adsorbate–surface interactions. By means of high-resolution, fast-scanning STM unprecedented new insight was recently achieved into a number of fundamental processes related to the interaction of largish molecules with surfaces such as molecular diffusion, bonding of adsorbates on surfaces, and molecular self-assembly. In addition to the normal imaging mode, the STM tip can also be employed to manipulate single atoms and molecules in a bottom–up fashion, collectively or one at a time. In this way, molecule-induced surface restructuring processes can be revealed directly and nanostructures can be engineered with atomic precision to study surface quantum phenomena of fundamental interest. Here we will present a short review of some recent results, several of which were obtained by our group, in which several features of the complex interaction between large organic molecules and metal surfaces were revealed. The focus is on experiments performed using STM and other complementary surface-sensitive techniques.

Bond-order discrimination by atomic force microscopy.

Visualizing Bond Order Bond lengths in conjugated molecules closely reflect individual bond order and are usually determined by diffraction methods. It is valuable to know bond order for rationalizing aromaticity, and reactivity and for chemical structure determination. Gross et al. (p. 1326; see the Perspective by Perez and the cover) differentiated the bond orders in individual molecules in the fullerene C60 and in polyaromatic hydrocarbons by imaging with noncontact atomic force microscopy (AFM). The molecules were adsorbed onto a copper surface, and the AFM tip was decorated with a CO molecule, which was used to measure tip frequency shifts above the bonds and their apparent lengths. Multiple bonds appeared brighter in the images because of stronger Pauli repulsion, and their shorter length was amplified by bending of the CO at the tip apex. Images detected with an atomic force microscope tip decorated with a carbon monoxide molecule could distinguish Pauling bond order. We show that the different bond orders of individual carbon-carbon bonds in polycyclic aromatic hydrocarbons and fullerenes can be distinguished by noncontact atomic force microscopy (AFM) with a carbon monoxide (CO)–functionalized tip. We found two different contrast mechanisms, which were corroborated by density functional theory calculations: The greater electron density in bonds of higher bond order led to a stronger Pauli repulsion, which enhanced the brightness of these bonds in high-resolution AFM images. The apparent bond length in the AFM images decreased with increasing bond order because of tilting of the CO molecule at the tip apex.

On-Surface Covalent Coupling in Ultrahigh Vacuum

The formation of 2D nanostructures through self-assembly on surfaces is a promising strategy for the fabrication of nanoscale devices by a bottom-up approach. Complex molecular structures held together by weak and reversible van der Waals interactions, hydrogen bonds, and metal complexation have been obtained under ultraclean conditions, namely in an ultrahigh vacuum (UHV). However, such structures are inherently fragile and the intermolecular interactions are weak, which precludes, for example, mechanical stability or intermolecular charge transport. Interconnection of the molecules in a controlled way directly on a surface through robust and irreversible covalent bonding offers a way to overcome these limitations. Such on-surface chemistry under ultraclean conditions potentially presents several advantages over solution synthesis: a) on-surface and UHV experiments allow a much broader range of reaction temperatures to be used: Sublimation cell or substrate temperatures can be easily controlled from 4 to 600 K without risk of air oxidation or solvent decomposition; b) the 2D confined geometry could favor some reactions or supramolecular aggregates that are not usually observed. These can arise as a result of entropic or kinetic effects or through interaction with the substrate; c) it could allow the preparation, from suitable small precursors, of extended 1D or 2D arrays of rigid oligomers or polymers that are impossible to synthesize in solution for solubility reasons; d) on-surface reactions can be followed by UHV scanning tunneling microscopy (STM). This powerful technique not only allows imaging at the submolecular level, but also very local spectroscopic measurements, tip-induced reactions, and molecular manipulation.

On-Surface Covalent Linking of Organic Building Blocks on a Bulk Insulator

On-surface synthesis in ultrahigh vacuum provides a promising strategy for creating thermally and chemically stable molecular structures at surfaces. The two-dimensional confinement of the educts, the possibility of working at higher (or lower) temperatures in the absence of solvent, and the templating effect of the surface bear the potential of preparing compounds that cannot be obtained in solution. Moreover, covalently linked conjugated molecules allow for efficient electron transport and are, thus, particularly interesting for future molecular electronics applications. When having these applications in mind, electrically insulating substrates are mandatory to provide sufficient decoupling of the molecular structure from the substrate surface. So far, however, on-surface synthesis has been achieved only on metallic substrates. Here we demonstrate the covalent linking of organic molecules on a bulk insulator, namely, calcite. We deliberately employ the strong electrostatic interaction between the carboxylate groups of halide-substituted benzoic acids and the surface calcium cations to prevent molecular desorption and to reach homolytic cleavage temperatures. This allows for the formation of aryl radicals and intermolecular coupling. By varying the number and position of the halide substitution, we rationally design the resulting structures, revealing straight lines, zigzag structures, and dimers, thus providing clear evidence for the covalent linking. Our results constitute an important step toward exploiting on-surface synthesis for molecular electronics and optics applications, which require electrically insulating rather than metallic supporting substrates.

Step-by-step rotation of a molecule-gear mounted on an atomic-scale axis

Gears are microfabricated down to diameters of a few micrometres. Natural macromolecular motors, of tens of nanometres in diameter, also show gear effects. At a smaller scale, the random rotation of a single-molecule rotor encaged in a molecular stator has been observed, demonstrating that a single molecule can be rotated with the tip of a scanning tunnelling microscope (STM). A self-assembled rack-and-pinion molecular machine where the STM tip apex is the rotation axis of the pinion was also tested. Here, we present the mechanics of an intentionally constructed molecule-gear on a Au(111) surface, mounting and centring one hexa-t-butyl-pyrimidopentaphenylbenzene molecule on one atom axis. The combination of molecular design, molecular manipulation and surface atomic structure selection leads to the construction of a fundamental component of a planar single-molecule mechanical machine. The rotation of our molecule-gear is step-by-step and totally under control, demonstrating nine stable stations in both directions.

Stepwise syntheses of mono- and di-nuclear ruthenium tpphz complexes [(bpy)2Ru(tpphz)]2– and [(bpy)2Ru(tpphz)Ru(bpy)2]4+{tpphz = tetrapyrido[3,2-a: 2′,3′-c: 3″,2″-h: 2″,3‴-j]phenazine}

The complex [(bpy)2Ru(tpphz)]2+(tpphz = tetrapyridophenazine), is obtained by reaction of [(bpy)2Ru(phendione)]2+with 5,6-diamino-1,10-phenanthroline; upon reaction with [(bpy)2Ru(Me2CO)2]2+, the fully conjugated dimer [(bpy)2Ru(tpphz)Ru(bpy)2]4+ is obtained.

Self-Assembly of Fivefold-Symmetric Molecules on a Threefold-Symmetric Surface†

Buckybowls: The adsorption of penta-tert-butylcorannulene, a molecule with fivefold symmetry, on Cu(111), a surface with threefold symmetry, is investigated by scanning tunneling microscopy complemented by structure calculations. The symmetry mismatch is resolved by the formation of threefold-symmetric subunits consisting of three molecules, which combine with single molecules to form a nearly perfect filling of the plane (see picture).

Low temperature manipulation of big molecules in constant height mode

The possibility of extending the lateral manipulation process performed with the tip of a scanning tunneling microscope at low temperature to large molecules is demonstrated. Single Cu–TBPP molecules deposited on a Cu substrate were manipulated by means of the interaction between the molecule and the tip. Due to the complicated structure of the molecules and to their high conductance, we have explored the possibilities of performing controlled lateral manipulation at constant height. On Cu(111) this method makes possible translation combined with rotation of the molecules on the surface.

Cu-TBPP and PTCDA molecules on insulating surfaces studied by ultra-high-vacuum non-contact AFM

The adsorption of two kinds of porphyrin (Cu-TBPP) and perylene (PTCDA) derived organic molecules deposited on KBr and Al2O3 surfaces has been studied by non-contact force microscopy in ultra-high vacuum, our goal being the assembly of ordered molecular arrangements on insulating surfaces at room temperature. On a Cu(100) surface, well ordered islands of Cu-TBPP molecules were successfully imaged. On KBr and Al2O3 surfaces, it was found that the same molecules aggregate in small clusters at step edges, rather than forming ordered monolayers. First measurements with PTCDA on KBr show that nanometre-scale rectangular pits in the surface can act as traps to confine small molecular assemblies.

Supramolecular architectures on surfaces formed through hydrogen bonding optimized in three dimensions.

Supramolecular self-assembly on surfaces, guided by hydrogen bonding interactions, has been widely studied, most often involving planar compounds confined directly onto surfaces in a planar two-dimensional (2-D) geometry and equipped with structurally rigid chemical functionalities to direct the self-assembly. In contrast, so-called molecular Landers are a class of compounds that exhibit a pronounced three-dimensional (3-D) structure once adsorbed on surfaces, arising from a molecular backboard equipped with bulky groups which act as spacer legs. Here we demonstrate the first examples of extended, hydrogen-bonded surface architectures formed from molecular Landers. Using high-resolution scanning tunnelling microscopy (STM) under well controlled ultrahigh vacuum conditions we characterize both one-dimensional (1-D) chains as well as five distinct long-range ordered 2-D supramolecular networks formed on a Au(111) surface from a specially designed Lander molecule equipped with dual diamino-triazine (DAT) functional moieties, enabling complementary NH...N hydrogen bonding. Most interestingly, comparison of experimental results to STM image calculations and molecular mechanics structural modeling demonstrates that the observed molecular Lander-DAT structures can be rationalized through characteristic intermolecular hydrogen bonding coupling motifs which would not have been possible in purely planar 2-D surface assembly because they involve pronounced 3-D optimization of the bonding configurations. The described 1-D and 2-D patterns of Lander-DAT molecules may potentially be used as extended molecular molds for the nucleation and growth of complex metallic nanostructures.