Thermodynamics, morphology and molecular structure of molecular compounds in trisamide triarylamine organogels and pseudo-organogels.

In this paper, potentially-gelling binary systems are investigated by DSC, X-ray and Electron microscopy in order to assess their gel status and the role of the Hansen solubility parameter. The low molecular weight organogelator is a Triarylamine Trisamide (TATA) while the solvents consist of a series of halogeno-ethanes and of toluene. Temperature-concentration phase diagrams are mapped out from DSC traces. They reveal the existence of one or more TATA/solvent molecular compounds. The X-ray data, that display different diffraction patterns depending on the solvent and the temperature, show the existence of different molecular structures, and thus confirm the outcome of the T-C phase diagram. Tentative molecular organizations are also discussed in light of previous results obtained in the solid state. The morphology by TEM on dilute systems, and TEM on more concentrated systems highlight the degree of physical cross-links, which leads one to regard some systems as pseudo-gels.

Light-Driven Molecular Motors Boost the Selective Transport of Alkali Metal Ions through Phospholipid Bilayers.

A hydrophobic light-driven rotary motor is functionalized with two 18-crown-6 macrocycles and incorporated into phospholipid bilayers. In the presence of this molecular construct, fluorescence assays and patch clamp experiments show the formation of selective alkali ion channels through the membrane. Further, they reveal a strongly accelerated ion transport mechanism under light irradiation. This increase of the fractional ion transport activity (up to 400%) is attributed to the out-of-equilibrium actuation dynamics of the light-driven rotary motors, which help to overcome the activation energy necessary to achieve translocation of alkali ions between macrocycles along the artificial channels.

Supramolecular Polymerization of Triarylamine-Based Macrocycles into Electroactive Nanotubes.

A S6-symmetric triarylamine-based macrocycle (i.e., hexaaza[16]paracyclophane), decorated with six lateral amide functions, is synthesized by a convergent and modular strategy. This macrocycle is shown to undergo supramolecular polymerization in o-dichlorobenzene, and its nanotubular structure is elucidated by a combination of spectroscopy and microscopy techniques, together with X-ray scattering and molecular modeling. Upon sequential oxidation, a spectroelectrochemical analysis of the supramolecular polymer suggests an extended electronic delocalization of charge carriers both within the macrocycles (through bond) and between the macrocycles along the stacking direction (through space).

Temperature Control of Sequential Nucleation-Growth Mechanisms in Hierarchical Supramolecular Polymers.

Upon cooling in solution, chiral triarylamine tris-amide unimers produce organogels by stacking into helical supramolecular polymers, which subsequently bundle into larger fibers. Interestingly, circular dichroism, vibrational circular dichroism, and AFM imaging of the chiral self-assemblies revealed that monocolumnar P-helical fibrils formed upon fast cooling, whereas bundled M-superhelical fibers formed upon slow cooling. The mechanistic study of this structural bifurcation reveals the presence of a strong memory effect, reminiscent of a complex stepwise combination of primary and secondary nucleation-growth processes. These results highlight the instrumental role of sequential self-assembly processes to control supramolecular architectures of multiple hierarchical order.

Supramolecular Electropolymerization.

Gaining control over supramolecular polymerization mechanisms is of high fundamental interest to understand self-assembly and self-organization processes at the nanoscale. It is also expected to significantly impact the design and improve the efficiency of advanced materials and devices. Up to now, supramolecular polymerization has been shown to take place from unimers in solution, mainly by variations of temperature or of concentration. Reported here is that supramolecular nucleation-growth of triarylamine monomers can be triggered by electrochemistry in various solvents. The involved mechanism offers new opportunities to precisely address in space and time the nucleation of supramolecular polymers at an electrode. To illustrate the potential of this methodology, supramolecular nanowires are grown an oriented over several tens of micrometers between different types of commercially available electrodes submitted to a single DC electric field, reaching a precision unprecedented in the literature.

Anisotropic Self-Assembly of Supramolecular Polymers and Plasmonic Nanoparticles at the Liquid-Liquid Interface.

The study of supramolecular polymers in the bulk, in diluted solution, and at the solid-liquid interface has recently become a major topic of interest, going from fundamental aspects to applications in materials science. However, examples of supramolecular polymers at the liquid-liquid interface are mostly unexplored. Here, we describe the supramolecular polymerization of triarylamine molecules and their light-triggered organization at a chloroform-water interface. The resulting interfacial nematic layer of these 1D supramolecular polymers is further used as a template for the precise alignment of spherical gold nanoparticles coming from the water phase. These hybrid thin films are spontaneously formed in a single process, without chemical prefunctionalization of the metallic nanoparticles, and their ordering is improved by centrifugation. The resulting polymer chains and strings of nanoparticles can be co-aligned with high anisotropy over very large distances. By using a combination of experimental and theoretical investigations, we decipher the full sequence of this oriented self-assembly process. In such a highly anisotropic configuration, electron energy loss spectroscopy reveals that the self-assembled nanoparticles behave as plasmonic waveguides.

Some Remarkable Rheological and Conducting Properties of Hybrid PVC Thermoreversible Gels/Organogels.

We report on investigations into the rheological properties of organogels prepared from triarylamine trisamide (TATA) and oligo phenylene vinylene (OPVOH) molecules in binary organogel gels and in ternary thermoreversible networks with poly vinyl chloride (PVC). In the case of OPVOH, we show that the modulus of the ternary gel is simply the sum of the modulus of each binary gel, corresponding to the so-called Voigt upper limit. In contrast, TATA/PVC ternary gels generally exceed the Voigt upper limit. In an attempt to account for this unexpected outcome, we hypothesized that a de-solvation process might occur in the PVC fibrils that possibly originates in the propensity of TATA molecules to form molecular compounds with the solvent. Finally, the conducting properties of TATA/solvent organogels and TAT/PVC/solvent reversible networks were measured. It was found that they strongly depend on the solvent type but are not significantly altered when PVC is present. Therefore, PVC gels can be made conducive by incorporating TATA fibers.

3D supramolecular self-assembly of [60]fullerene hexaadducts decorated with triarylamine molecules.

A clickable fullerene hexa-adduct scaffold has been functionalized with twelve triarylamine subunits. The light-triggered self-assembly of this molecular unit leads to 3D honeycomb-like structures with inner pores of around 10 nm diameter. Multiple grafting of triarylamine subunits onto a hard-core C60 unit increases the dimensionality of the self-assembly process by reticulating the 1D nanowires typically obtained from the supramolecular polymerization of triarylamine monomers.