Impact of chirality on the aggregation modes of L-phenylalanine- and D-glucose-decorated phenylene-thiophene oligomers

The aggregation modes of three L-phenylalanine- or D-glucose-functionalized phenylene-thiophene oligomers have been investigated by UV-Vis absorption and electronic circular dichroism (ECD) spectroscopies in different conditions of solution aggregation and thin...

Hierarchical self-assembly and controlled disassembly of a cavitand-based host–guest supramolecular polymer

Two hierarchical aggregation modes of cavitand-based supramolecular polymers allow implementing orthogonal disassembly procedures: electrochemical reduction for linear chains and solvent-driven dissolution for bundles.

Control of the hierarchical self-assembly of polyoxometalate-based metallomacrocycles by redox trigger and solvent composition

Discrete metallomacrocycles are attractive scaffolds for the formation of complex supramolecular architectures with emergent properties. We herein describe the formation of hierarchical nanostructures using preformed metallomacrocycles by coordination-driven self-assembly of a covalent organic–inorganic polyoxometalate (POM)-based hybrid. In this system, we take advantage of the presence of charged subunits (POM, metal linker, and counterions) within the metallomacrocycles, which drive their aggregation through intermolecular electrostatic interactions. We show that the solvent composition and the charge of the metal linker are key parameters that steer the supramolecular organization. Different types of hierarchical self-assemblies, zero-dimensional (0D) dense nanoparticles, and 1D worm-like nanoobjects, can be selectively formed owing to different aggregation modes of the metallomacrocycles. Finally, we report that the worm-like structures drastically enhance the solubility in water of a pyrene derivative and can act as molecular carriers.

Aggregation modes of anionic oxacarbocyanines with polycations in solution and in ESAMs

Interaction of oxacarbocyanines D-G with three polycations in aqueous solutions results in the formation of two types of likely small, distorted aggregates rather than the classical J aggregates. On the contrary, the latter are extensively and almost exclusively obtained in electrostatically self-assembled multilayers (ESAMs) prepared by alternate polycation/dye adsorption on quartz substrates. The J-aggregate growth on supported polycations is qualitatively shared by the four cyanines, a fact that reveals the crucial role of the double anionic substitutions on the dyes. On the other hand, films with D and E, which are known to have a stronger tendency to give dimers in water, exhibit higher J-band intensities and stability upon drying relative to those with F and G. Based on these observations, we suggest that energetic factors associated with cofacial dye/dye van der Waals interactions, ultimately related with the degree of planarity of the conjugated chromophores, may still play a major role in controlling aggregation equilibria in these complex systems.