We have observed the inversion of the solvation environment of ao ne-dimensional solid by low-temperature scanning tunneling microscopy. Adsorption of 3-methoxy-9diazofluorene on Ag(111) yields highly oriented supramolecular chains,w hich are then exposed to water molecules.T he annealing of dry and water-decorated chains results in diametrically opposed outcomes.While the former simply leads to an increase in chain length and number,t he latter results in acomplete loss of order and produces water clusters decorated with the organic molecule.

Low-temperature scanning tunneling microscopy was used to follow the formation of a solvation shell around an adsorbed functionalized azo dye from the attachment of the first water molecule to a fully solvated molecule. Specific functional groups bind initially one water molecule each, which act as anchor points for additional water molecules. Further water attachment occurs in areas close to these functional groups even when the functional groups themselves are already saturated. In contrast, water molecules surround the hydrophobic parts of the molecule only when the two-dimensional solvation shell closes around them. This study thus traces hydrophilic and hydrophobic properties of an organic molecule down to a sub-molecular length scale.

Metal carbenes are key intermediates in a plethora of homogeneous and heterogeneous catalytic processes. However, despite their importance to heterogeneous catalysis, the influence of surface attachment on carbene reactivity has not yet been explored. Here, we reveal the interactions of fluorenylidene (FY), an archetypical aromatic carbene of extreme reactivity, with a Ag(111) surface. For the first time, the interaction of a highly reactive carbene with a metal surface could be studied by scanning tunneling microscopy (STM). FY chemisorbs on Ag(111) with an estimated desorption energy of 3 eV, forming a surface bound silver−carbene complex. The surface interaction leads to a switching of the electronic ground state of FY from triplet to singlet, and to controlled chemical reactivity. This atomistic understanding of the interplay between carbenes and metal surfaces opens the way for the development of novel classes of catalytic systems based on surface metal carbenes.

We observe the transformation of fractal ice islands grown at 96 K to compact ones annealed at 118 K and compare those to compact islands grown directly at 118 K. The low-temperature grown islands form a four bilayer high wetting layer. The annealing causes a crystallization and reshaping of the islands and a substantial increase in height and roughness in particular at higher coverage. Moreover, it leads to a dewetting of the ice film. The islands grown at the higher temperature show qualitative similarities to the annealed ones at smaller nucleation density. However, their orientation with respect to the surface differs by 30° as compared to the annealed islands.

We investigate the polymorphism of complexes formed by the hydration of a functionalized azobenzene molecule by low-temperature scanning tunneling microscopy. Under conditions at which the water-less azobenzene molecules remain as monomers on Au(111), co-adsorption of water leads to water–azobenzene complexes. These complexes prefer to adopt linear arrangements of the azobenzene mediated by its functionalized end groups. Such structures may serve as model systems for investigating the influence of a solvent on a surface reaction.