Influence of water on supra-molecular assembly of 4, 4'-dihydroxy azobenzene on Ag(111).

We explore co-deposition of water and 4, 4'-dihydroxy azobenzene on Ag(111) by low-temperature scanning tunneling microscopy at different water-to-azobenzene ratios. At all ratios, the water interacts with the hydroxyl end groups of the molecule replacing the direct hydrogen bonding. The change in bonding reduces the azobenzene density as compared to the one in the closed-packed waterless azobenzene structure. At intermediate water-to-azobenzene ratios, pores are formed in the azobenzene layer at nanometer distance from the water. At high water-to-azobenzene ratios, a water superstructure with a 1.4 nm × 1.4 nm unit cell develops. Our results point to a method to vary the density of an organic layer by tuning the amount of an inorganic additive.

Using the first steps of hydration for the determination of molecular conformation of a single molecule.

Determination of the exact structure of individual molecules is the ultimate goal of high-resolution microscopy. However, the resolution of scanning tunneling microscopy (STM) is intrinsically limited to the extent of molecular orbitals, which frequently do not differ for small changes in the molecular conformation. Here we use the position of water molecules during the first hydration steps of an azobenzene derivative on Au(111) to determine not only the orientation of the end groups with respect to the phenyl rings but also the orientation of the two phenyl rings with respect to the azo group. We investigate the co-adsorption of 4,4'-hydroxy-azobenzene and water molecules on Au(111) by low-temperature STM. The water molecules are attached exclusively to the hydroxyl end groups of the azobenzene derivatives. Predominantly the trans-azobenzene molecule with the two hydroxyl groups pointing into opposite directions is adsorbed. As corroborated by the attachment of a single water molecule to 4-anilino-4'-nitro azobenzene on the same inert surface, the method is generally applicable for structure determination of molecules with appropriate end groups. Our study thus gives unprecedented information about the intramolecular orientation based on the first real space observation of the hydration of a functional molecule.

Reorientation of a single bond within an adsorbed molecule by tunneling electrons.

Scanning tunneling microscopy offers the exciting possibility to manipulate individual molecules by vibrational excitation via inelastically tunneling electrons. The electrons transfer energy into molecular vibrational modes, leading to breakage or formation of individual bonds. It is challenging to precisely control intramolecular changes by this process. We demonstrate that for 4,4'-dihydroxyazobenzene adsorbed on Au(111) or Ag(111), the manipulation facilitates rotation of the OH end groups around the C-O bond between metastable states; this corresponds to a reorientation of the hydrogen, the ultimate limit of a conformational change within a molecule.

Coulomb attraction during the carpet growth mode of NaCl.

The submonolayer growth of NaCl bilayer high-rectangular shaped islands on Ag(111) is investigated at around room temperature by using low temperature scanning tunneling microscopy. The growth at the step edges is preferred. Two kinds of islands are observed. They either grow with their non-polar edge at the step edge of Ag(111) or the islands overgrow in a carpet-like mode with the polar direction parallel to the edge. In the latter case, the Ag step is rearranged and considerable, while the NaCl layer is bent. This study clarifies the nature of the interaction of an alkali halide nanostructure with a metal step edge.

The frontier orbitals of a push-pull azobenzene adsorbed on a metal surface in different bonding geometries investigated by scanning tunneling spectroscopy and spectroscopy mapping.

The electronic structure of 4-anilino-4'-nitroazobenzene superstructures formed on Au(111) at 250 K is investigated by low temperature scanning tunneling microscopy, scanning tunneling spectroscopy, and dI/dV mapping at 5 K. Changes in the dI/dV maps of this push-pull molecule reflect the spatial distribution of the frontier orbitals on the molecular scale. Spectra of the trans- and the cis∗-isomer differ between themselves and in different parts of supramolecular assemblies. The relative importance of these differences is discussed.

Light driven reactions of single physisorbed azobenzenes.

We present a successful attempt of decoupling a dye molecule from a metallic surface via physisorption for enabling direct photoisomerization. Effective switching between the isomers is possible by exposure to UV light via the rotation pathway.

Isomerization of an azobenzene derivative on a thin insulating layer by inelastically tunneling electrons.

Scanning tunneling microscopy is used to investigate isomerization of amino-nitro-azobenzene on a thin NaCl layer on Ag(111) by inelastically tunneling electrons. A reversible isomerization between a planar trans and a three-dimensional cis form with two different thresholds is demonstrated. The isomerization characteristics are rationalized in terms of binding of the multipolar molecule to the ionic layer. This study shows the feasibility of a bistable single molecule switch on an insulator.

An electron induced two-dimensional switch made of azobenzene derivatives anchored in supramolecular assemblies.

Supramolecular assemblies of 4-anilino-4'-nitroazobenzene are investigated on the Au(111) surface by low temperature scanning tunneling microscopy and spectroscopy with submolecular resolution. Adsorption at 250 K leads to three different structures that are formed via hydrogen bonds: a star structure and two types of line structures: a meandering and a zigzag line. The formation of these supramolecular assemblies is affected by the available space on the fcc domains of the reconstructed Au(111) substrate as well as by the two-dimensional chirality of the molecules on the surface. The star structure is enantiomerically pure, while both types of lines consist of a racemic mixture. Bonding between homochiral pairs differ from the one between heterochiral pairs in the position of the hydrogen bonds. Inside these supramolecular assemblies two configurations of the molecules are identified: An almost straight trans-configuration and a slightly bent cis*-configuration. The trans-configuration largely reflects the structure of this isomer in gas phase, while the cis*-configuration is two-dimensional on the surface in contrast to the three-dimensional gas phase cis-configuration. The reversible trans-cis* isomerization is induced by electron tunneling through the LUMO+1 state of the molecule, which is located at +2.9 V.