Molecule-molecule versus molecule-substrate interactions in the assembly of oligothiophenes at surfaces.

In this paper we present a joint experimental and theoretical approach for the study of the assembly of end-substituted oligothiophenes at surfaces with different polarities (i.e., mica vs graphite). Scanning probe microscopy studies of (sub)monolayer deposits show various types of structures (one-dimensional fibrils, two-dimensional regular layers, and monolayers), depending on the nature of the end groups and the substrate. Using molecular modeling with an atomistic approach, we focus on the interplay between the molecule-molecule (and segment-segment) interactions and the molecule-substrate interactions and their influence on the observed morphologies and the stacking geometry. Such information is relevant for controlling the structural order in thin layers of thiophene oligomers for use in field-effect transistor applications, for example, by modifying the nature of dielectric material over which those compounds are deposited.

Synthesis, separation, and isomer-dependent packing in two dimensions--detected by scanning tunnelling microscopy--of a TTF derivative.

The synthesis, isolation and STM imaging on graphite of the cis and trans isomers of a TTF reveal isomer-dependent packing, and constitutes a way to study the non-covalent interactions at play in these systems.

Submolecular visualisation of palladium acetate complexation with a bipyridine derivative at a graphite surface.

In situ complexation of palladium acetate by a monolayer of a bipyridine derivative at a graphite/liquid interface has been observed using scanning tunneling microscopy.

Novel chitosan-ZnO based nanocomposites as luminescent tags for cellulosic materials.

Novel chitosan-ZnO composites have been synthesized as luminescent taggants for cellulosic materials. The synthesized chitosan-ZnO nanospheres (CS-ZnO NS), chitosan-ZnO-oleic acid quantum dots (CS-ZnO-oleic QD) and chitosan-ZnO-oleic acid:Eu(3+) doped nanorods (CS-ZnO-oleic:Eu(3+) NR) were characterized by X-ray diffraction, photoluminescence spectroscopy, FTIR spectroscopy and transmission electron microscopy. The prepared luminescent CS-ZnO composites were used in printing paste and applied to different types of papers and textiles by using screen printing technique. The colorimetric values of the printed CS-ZnO-oleic acid and CS-ZnO-oleic:Eu(3+) showed that printing caused slightly change in color values. Scanning electron microscopy images and color values of the printed surface showed that CS-ZnO-oleic QD and highly luminescence CS-ZnO-olic:Eu(3+) NR are suitable for use as a printed security feature.

Influence of halogen substituents on the self-assembly of oligothiophenes--a combined STM and theoretical approach.

Iodinated quaterthiophenes 2-3 have been synthesized and their self-assembling behavior investigated at the liquid-solid interface by means of high-resolution scanning tunneling microscopy in comparison to parent oligothiophene 1. All three compounds spontaneously give well-ordered 2D crystalline monolayers at the graphite surface and order in a lamella-type arrangement of the conjugated backbones concomitant with an interlocking of the alkyl side chains. Symmetrically substituted oligothiophenes 1 and 3 without a relevant dipole moment self-assemble in a similar fashion, exhibiting comparable unit cells, whereas monoiodo derivative 2 arranges as pairs along the lamella axis due to the presence of a permanent dipole moment induced by the polarizable halogen group. Corroborated by quantum chemical calculations, novel head-to-head (iodo-iodo) intermolecular interactions were found to take place for this unsymmetrical derivative. The investigation of mixed solutions clearly reveals that at the solid-liquid interface a homogeneous layer of this compound is formed, which comprises the highest packing density leading to a separation process at the interface.

A nanoscale view of supramolecular stereochemistry in self-assembled monolayers of enantiomers and racemates.

The effect that molecular chirality has on the formation of monolayer structures by pure enantiomers and their racemates at the liquid/solid interface has been investigated for two chiral compounds (1 and 2) which differ from each other by the presence or absence of an ester function in their respective molecular structures. 1 shows pseudoracemate formation when the achiral graphite support is exposed to a solution containing a racemate while 2 shows racemic conglomerate formation. This difference is rationalized in terms of the orientation of the pure enantiomers with respect to the graphite substrate and highlights the importance of molecular structure and its influence on balancing the interplay between molecular conformation and molecular packing on the surface. For 1, nonstoichiometric mixtures of both enantiomers have been investigated, and the results are discussed in the framework of the sergeant and soldiers principle. These results are important for the understanding and prediction of spontaneous resolution in monolayer systems.

Metal ion complexation: a route to 2 D templates?

The two-dimensional ordering of a number of 2,2'-bipyridine derivatives at the liquid/solid interface has been investigated by scanning tunneling microscopy. By appropriate functionalization of the bipyridine units, their intermolecular distance can be tuned, which has proved to be crucial for complexation with metal ions. The in situ addition of metal salts (Pd(2+), Cu(2+)), leading to the formation of metal-bipyridine complexes, has a dramatic influence on the two-dimensional ordering of the molecules and suggests that these complexes could be used as templates.