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Markus Lackinger

Publications and source records attributed to Markus Lackinger.

6 recordsLinked to original sources

Solvent induced polymorphism in supramolecular 1,3,5-benzenetribenzoic acid monolayers.

This work presents a scanning tunneling microscopy (STM) based study of benzenetribenzoic acid (BTB) monolayer structures at the liquid-solid interface. On graphite(0001) the tailored molecules self-assemble into 2D supramolecular host systems, suitable for the incorporation of other nanoscopic objects. Two crystallographically different BTB structures were found-both hydrogen bonded networks. A specific structure was deliberately selected by solvent identity. One of the BTB polymorphs is a 6-fold chicken-wire structure with circular, approximately 2.8 nm wide cavities. The other structure exhibits an oblique unit cell and a different hydrogen bonding pattern. The large cavity size of the chicken-wire structure was made possible through comparatively strong 2-fold hydrogen bonds between carboxylic groups. In addition, the low conformational flexibility of BTB was supportive to combat the tendency for dense packing.

Journal Article↗

Mediated coadsorption at the liquid-solid interface: Stabilization through hydrogen bonds.

Stable adsorption of 1,3,5-tris(4-pyridyl)-2,4,6-triazine (TPT) molecules from the liquid phase was only observed in binary solutions, that is, in the presence of a second (adsorptive) species. The process of mediated coadsorption of a molecular species at the liquid-solid interface was accomplished through complexation of TPT with a second type of molecule acting as a "molecular glue" via hydrogen bonds. Scanning tunneling microscopy (STM) was utilized to investigate the structure of the coadsorbed monolayers at the liquid-solid interface. Trimesic acid (TMA) and terephthalic acid (TPA)--both benzene rings with disposed carboxylic acid groups-were appropriate to precipitate the stable adsorption of TPT. According to the different symmetry and number of carboxylic acid groups, various networks were observed.

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Self-assembly of trimesic acid at the liquid-solid interface-a study of solvent-induced polymorphism.

A scanning tunneling microscope operated under ambient conditions was utilized to study the self-assembly of trimesic acid (TMA) at the liquid-solid interface. On a graphite substrate, two different open, loosely packed, two-dimensional hydrogen-bond networks were found. Both structures exhibit a periodic arrangement of approximately 1.0 nm wide cavities, which can be used for the co-adsorption of another species (guest) within the cells of this host system. These two polymorphs ("chickenwire" and "flower" structures) differ in their molecular packing density and hydrogen-bonding schemes. Using a homologous series of alkanoic acids as solvents, ranging from butyric to nonanoic, selective self-assembly of either the "flower" or "chickenwire" forms was achieved on a graphite surface. Solubility of TMA in these acid solvents was found to decrease with increasing chain length, and the longer-chain solvents favored formation of the chickenwire polymorph structure on the surface.

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Dynamics of grain boundaries in two-dimensional hydrogen-bonded molecular networks.

The temporal evolution of domain boundaries of hydrogen-bonded molecular monolayers at the liquid-solid interface is evaluated by recording series of subsequent scanning tunneling microscopy (STM) images. Comparison of dissimilar benzene carboxylic acids reveals a clear distinction between one- and two-dimensional H-bonded network structures. Trimesic acid forms a two-dimensionally H-bonded networked structure, whereas terephthalic acid organizes in a dense packing of H-bonded linear chains on a graphite surface. In addition, TMA forms a sixfold lattice on a threefold graphite substrate, whereas TPA exhibits only a twofold lattice, causing a high grain-boundary line energy for the latter. In the case of TMA the nanostructure was mostly stable during the observation time. For TPA, Ostwald ripening-that is, the growth of larger islands at the expense of smaller islands-was observed. To explain the various experimentally observed timescales of the dynamics occurring at grain boundaries, molecular mechanics simulations were applied to calculate the binding energy of edge molecules, that is, the line energy, of finite islands of both trimesic and terephthalic acid on a graphite substrate.

Adsorption↗

Incorporation and manipulation of coronene in an organic template structure.

A two-dimensional molecular template structure of 1,3,5-benzenetricarboxylic acid (trimesic acid, TMA) was formed on a highly oriented pyrolytic graphite surface (HOPG) by self-assembly at the liquid-solid interface. Scanning tunneling microscopy (STM) investigations show high-resolution images of the porous structure on the surface. After the host structure was created, coronene molecules were inserted as guest molecules into the pores. STM results indicate that some of the guest molecules rotate inside their molecular bearing. Further investigations show that single coronene molecules can be directly kicked out of their pores by means of STM.

Hydrogen Bonding↗

STM and STS of coronene on HOPG 0001 in UHV - adsorption of the smallest possible graphite flakes on graphite.

The adsorption of the aromatic molecule hexabenzobenzene (coronene) on an HOPG(0001) surface was investigated under UHV conditions by means of variable temperature scanning tunneling microscopy (STM) and spectroscopy (STS). Imaging on a mesoscopic scale showed a distribution of coronene islands. These islands are mobile on the surface and can be pinned at step-edges. Zooming in on areas apart from the islands reveals an hexagonal arrangement of coronene molecules in a closed layer. Submolecular resolved molecules consist of bright spots with varying intensity. This variation in intensity is explained with the commensurability of the adlayer. STS investigations were performed for various tip-sample distances, adjusted by the tunneling current setpoint. A gap can be seen for every setpoint, but its width is dependent on the setpoint. The gap for the largest tip-sample distance and therefore the smallest tip-sample interaction is compared with the theoretical value.

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