Molecular organization of cylindrical sexithiophene aggregates measured by X-ray scattering and magnetic alignment.

We have determined the internal organization of elongated sexithiophene aggregates in solution by combining small-angle X-ray scattering and magnetic birefringence experiments. The different aggregate axes can be probed independently by performing the experiments on magnetically aligned aggregates. We have found multiwalled cylindrical aggregates consisting of radially oriented sexithiophene molecules with pi-pi-stacking in the tangential direction, a structure that is considerably different from those previously found in other solvents. The aggregate morphology of this semiconducting material can thus be tuned by using different solvents, which offers the attractive perspective to steer chemical self-assembly toward nanostructures with desired functionalities, especially in combination with the alignment in a magnetic field.

The role of heterogeneous nucleation in the self-assembly of oligothiophenes.

The cooperative self-assembly of oligothiophenes can be characterized by heterogeneous nucleation caused by trace amounts of impurities leading to a manifold of supramolecular arrangements.

Chiral amphiphilic self-assembled alpha,alpha'-linked quinque-, sexi-, and septithiophenes: synthesis, stability and odd-even effects.

The synthesis, characterization, and self-assembly in butanol of a series of well-defined alpha,alpha'-linked quinqui-, sexi-, and septithiophenes substituted, via ester links at their termini, by chiral oligo(ethylene oxide) chains carrying an alpha, beta, delta, and epsilon methyl, respectively, are reported. Studies of the self-assembly of these molecules using UV/visible absorption, luminescence, and circular dichroism spectroscopies reveal, for the sexithiophene case, that the magnitude of the observed Cotton effect in the aggregates diminishes progressively as the chiral substituent is moved away from the thiophene segment. The stability of the assemblies increases with the length of the oligothiophene and as the substituent chiral unit is moved away from the aromatic core, being greatest for the unsubstituted case. The sign of the Cotton effect alternates in an "odd/even" manner as the position of the chiral substituent is moved along the oligo(ethylene oxide) chain and on going from the quinquethiophene to the septithiophene having the same side chain. Atomic force microscopy on materials deposited from solution on an aluminum or glass surface and optical measurements show that capsules are formed from the oligothiophenes with H-type packing of the aromatic segments.

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.

Magnetic deformation of self-assembled sexithiophene spherical nanocapsules.

We report the experimental observation of magnetic field deformation of spherical nanocapsules, self-assembled from sexithiophene molecules, into oblate spheroids, confirming a long-standing theoretical prediction. The magnetically deformed objects can be trapped in a compatible organogel to make them suitable for further investigations and applications. Our results show that strong magnetic forces can be effectively used, in a contact-free manner, as a tool to control the self-organization of a whole class of functional organic molecules.