Triarylamine-Based Supramolecular Polymers: Structures, Dynamics, and Functions.

Triarylamine molecules and triarylamine-based covalent polymers have been extensively investigated for more than 60 years in academics and industry because of their intriguing electronic and optical characteristics. However, despite the profusion of studies made on these derivatives, only very recently have the first examples of supramolecular polymers based on the triarylamine motif been described in the literature. Specifically, our research group has shown that, by adding supplementary hydrogen bonding moieties such as amide functions in their periphery, it becomes possible to tightly pack triarylamine molecules in columnar supramolecular stacks presenting a collinear arrangement of their central nitrogen atoms. These supramolecular polymers can self-assemble into various soft hierarchical structures such as helical fibers, nanorods, nanospheres, and nanoribbons in the sol and in the gel states, into liquid-crystalline mesophases, and into highly organized supramolecular frameworks and single crystals thereof. Interestingly, the associated supramolecular polymerization mechanism involves a nucleation step of high activation energy, which requires the flattening of the triarylamine core. Because of this singularity and although dependent on the precise chemical nature of the building blocks, it has been demonstrated that their supramolecular polymerization can be triggered by original tools, such as light irradiation or electrochemistry, and that it can display autocatalytic growth behaviors, remarkably strong amplifications of chirality, and complex and competing thermodynamic and kinetic self-assembly pathways. Further, from a functional point of view, it has been highlighted that a partial oxidation of the triarylamine molecules results in an enhanced through-space delocalization of the charge carriers along the π-π stacked supramolecular polymers, a feature that confers to these nanowires exceptional transport properties. Upon increasing the charge carrier concentration, the electronic nature of these soft materials can be switched from semiconducting to metallic behavior, and the presence of highly delocalized unpaired electrons in supramolecular polaronic band structures has been further exploited to implement plasmonic properties within subwavelength organic interconnects and microscopic optical waveguides. Finally, by making use of the unusual dynamics and functions of triarylamine-based nanostructures, it becomes possible to precisely address their self-construction within confined environments or within nano- and micrometer scale devices. This has been demonstrated for instance between nanoparticles and between electrodes, inside inorganic nanopores, and inside phospholipid bilayers, as well as at the liquid-liquid interface. Such a meeting point between bottom-up and top-down technologies is of high interest to envision further developments and applications for this entirely new class of supramolecular polymers, which combine a unique relationship between their structures, their dynamics, and their subsequent emerging functional properties.

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.

Nonlinear Kinetic Behavior in Constitutional Dynamic Reaction Networks.

Creating synthetic chemical systems which emulate the complexity observed in cells relies on exploiting chemical networks exhibiting nonlinear kinetic behavior. While control over reaction complexity using synthetic gene regulatory networks and DNA nanotechnology has developed greatly, little control exists over small molecule reaction networks. Toward this goal, we demonstrate a general framework for inducing nonlinear kinetic behavior in dynamic chemical networks based on molecules containing reversible chemical bonds. Specifically, this strategy relies on constituent species with differing thermodynamic stabilities that readily exchange components at rates that are faster than their formation rates. Such nonlinear networks (NLN) readily lead to sigmoidal kinetic profiles as a function of the relative thermodynamic stabilities of the constituent species. Furthermore, this behavior could be readily extended to more complex mixtures while maintaining nonlinearity. The generality of this method opens the possibility to generate nonlinear networks using a broad range of small molecule structures.

Adaptive Chemical Networks under Non-Equilibrium Conditions: The Evaporating Droplet.

Non-volatile solutes in an evaporating drop experience an out-of-equilibrium state due to non-linear concentration effects and complex flow patterns. Here, we demonstrate a small molecule chemical reaction network that undergoes a rapid adaptation response to the out-of-equilibrium conditions inside the droplet leading to control over the molecular constitution and spatial arrangement of the deposition pattern. Adaptation results in a pronounced coffee stain effect and coupling to chemical concentration gradients within the drop is demonstrated. Amplification and suppression of network species are readily identifiable with confocal fluorescence microscopy. We anticipate that these observations will contribute to the design and exploration of out-of-equilibrium chemical systems, as well as be useful towards the development of point-of-care medical diagnostics and controlled deposition of small molecules through inkjet printing.

Long-Range Energy Transport via Plasmonic Propagation in a Supramolecular Organic Waveguide.

Energy transport in organic materials is dependent on the coherent migration of optically induced excited states. For instance, in active organic waveguides, the tight packing of dye molecules allows delocalization of excitons over a distance generally limited to at most several hundred nanometers. Here, we demonstrate an alternative mechanism of energy transport in a triarylamine-based supramolecular organic waveguide that is plasmonic in nature and results in coherent energy propagation superior to 10 µm. The optical, electric, and magnetic properties of the doped material support the presence of metallic electrons that couple with and transport incident light. These results show that organic metals constitute a novel class of materials with efficient energy transport and are of potential interest for optoelectronics, plasmonics, and artificial light-energy harvesting systems.

Supramolecular Organic Nanowires as Plasmonic Interconnects.

Metallic nanostructures are able to interact with an incident electromagnetic field at subwavelength scales by plasmon resonance which involves the collective oscillation of conduction electrons localized at their surfaces. Among several possible applications of this phenomenon, the theoretical prediction is that optical circuits connecting multiple plasmonic elements will surpass classical electronic circuits at nanoscale because of their much faster light-based information processing. However, the placement and coupling of metallic elements smaller than optical wavelengths currently remain a formidable challenge by top-down manipulations. Here, we show that organic supramolecular triarylamine nanowires of ≈1 nm in diameter are able to act as plasmonic waveguides. Their self-assembly into plasmonic interconnects between arrays of gold nanoparticles leads to the bottom-up construction of basic optical nanocircuits. When the resonance modes of these metallic nanoparticles are coupled through the organic nanowires, the optical conductivity of the plasmonic layer dramatically increases from 259 to 4271 Ω(-1)·cm(-1). We explain this effect by the coupling of a hot electron/hole pair in the nanoparticle antenna with the half-filled polaronic band of the organic nanowire. We also demonstrate that the whole hybrid system can be described by using the abstraction of the lumped circuit theory, with a far field optical response which depends on the number of interconnects. Overall, our supramolecular bottom-up approach opens the possibility to implement processable, soft, and low cost organic plasmonic interconnects into a large number of applications going from sensing to metamaterials and information technologies.

Supramolecular self-assembly and radical kinetics in conducting self-replicating nanowires.

By using a combination of experimental and theoretical tools, we elucidate unique physical characteristics of supramolecular triarylamine nanowires (STANWs), their packed structure, as well as the entire kinetics of the associated radical-controlled supramolecular polymerization process. AFM, small-angle X-ray scattering, and all-atomic computer modeling reveal the two-columnar "snowflake" internal structure of the fibers involving the π-stacking of triarylamines with alternating handedness. The polymerization process and the kinetics of triarylammonium radicals formation and decay are studied by UV-vis spectroscopy, nuclear magnetic resonance and electronic paramagnetic resonance. We fully describe these experimental data with theoretical models demonstrating that the supramolecular self-assembly starts by the production of radicals that are required for nucleation of double-columnar fibrils followed by their growth in double-strand filaments. We also elucidate nontrivial kinetics of this self-assembly process revealing sigmoid time dependency and complex self-replicating behavior. The hierarchical approach and other ideas proposed here provide a general tool to study kinetics in a large number of self-assembling fibrillar systems.

Healable supramolecular polymers as organic metals.

Organic materials exhibiting metallic behavior are promising for numerous applications ranging from printed nanocircuits to large area electronics. However, the optimization of electronic conduction in organic metals such as charge-transfer salts or doped conjugated polymers requires high crystallinity, which is detrimental to their processability. To overcome this problem, the combination of the electronic properties of metal-like materials with the mechanical properties of soft self-assembled systems is attractive but necessitates the absence of structural defects in a regular lattice. Here we describe a one-dimensional supramolecular polymer in which photoinduced through-space charge-transfer complexes lead to highly coherent domains with delocalized electronic states displaying metallic behavior. We also reveal that diffusion of supramolecular polarons in the nanowires repairs structural defects thereby improving their conduction. The ability to access metallic properties from mendable self-assemblies extends the current understanding of both fields and opens a wide range of processing techniques for applications in organic electronics.

Anti-social punishment can prevent the co-evolution of punishment and cooperation.

The evolution of cooperation is one of the great puzzles in evolutionary biology. Punishment has been suggested as one solution to this problem. Here punishment is generally defined as incurring a cost to inflict harm on a wrong-doer. In the presence of punishers, cooperators can gain higher payoffs than non-cooperators. Therefore cooperation may evolve as long as punishment is prevalent in the population. Theoretical models have revealed that spatial structure can favor the co-evolution of punishment and cooperation, by allowing individuals to only play and compete with those in their immediate neighborhood. However, those models have usually assumed that punishment is always targeted at non-cooperators. In light of recent empirical evidence of punishment targeted at cooperators, we relax this assumption and study the effect of so-called 'anti-social punishment'. We find that evolution can favor anti-social punishment, and that when anti-social punishment is possible costly punishment no longer promotes cooperation. As there is no reason to assume that cooperators cannot be the target of punishment during evolution, our results demonstrate serious restrictions on the ability of costly punishment to allow the evolution of cooperation in spatially structured populations. Our results also help to make sense of the empirical observation that defectors will sometimes pay to punish cooperators.