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International audience; A S6-symmetric triarylamine-based macrocycle (i.e. hexaaza[16]para-cyclophane), 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 modelling. 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 macrocycles along the stacking direction (through space).

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.

Triarylamine molecules appended with crown-ethers or carboxylic moieties form self-assembled supramolecular channels within lipid bilayers. Fluorescence assays and voltage clamp studies reveal that the self-assemblies incorporating the crown ethers work as single channels for the selective transport of K+ or Rb+. The X-ray crystallographic structures confirm the mutual columnar self-assembly of triarylamines and crown-ethers. The dimensional fit of K+ cations within the 18-crown-6 leads to a partial dehydration and to the formation of alternating K+ cation-water wires within the channel. This original type of organization may be regarded as a biomimetic alternative of columnar K+-water wires observed for the natural KcsA channel. Supramolecular columnar arrangement was also shown for the triarylamine-carboxylic acid conjugate. In this latter case, stopped-flow light scattering analysis reveals the transport of water across lipid bilayer membranes with a relative water permeability as high as 17 μm s–1.

C3 -Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups, undergo supramolecular polymerization and further gelation by π-π stacking and hydrogen bonding of their TATA cores. By using subsequent ring-opening metathesis polymerization, these physical gels are permanently crosslinked into chemical gels. Detailed comparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by optical spectroscopies, electronic spectroscopies, atomic force microscopy, electronic paramagnetic resonance spectroscopy, X-ray scattering, electronic transport measurements, and rheology. The results presented here clearly evidence that the core structure of the functional supramolecular polymers can be precisely retained during the covalent capture whereas the mechanical properties of the gels are concomitantly improved, with an increase of their storage modulus by two orders of magnitude.

Upon cooling insolution, 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.

International audience; 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.

Bistable [ c2]daisy chain rotaxanes represent a particularly intriguing class of interlocked molecules that can produce internal sliding movements with a net contraction or extension at the single-molecule level. These nanometric motions show some analogies with the sliding motions of actin and myosin filaments in sarcomeres, and this is why [ c2]daisy chain rotaxanes have been also named as “molecular muscles,” as their first synthesis in 2000. In this minireview, the authors discuss the recent history of these molecules, their modular chemical structures, and the various synthetic pathways described in the literature to access them. The authors also detail how their internal motions can be controlled and characterized by a number of chemical and physical tools. The authors finally show that their integration within polymers and materials can give access to synchronized motions and amplifications up to the macroscopic scale. Overall, the numerous examples that have been described in the literature to date demonstrate that this family of molecules has already strongly influenced the entire field of research on artificial molecular machines, and has the potential to be implemented as actuators working at all scales, from nanometric-switchable devices to mechanically active soft matter materials.

A dendritic unit based on a benzenetricarboxamide core and three triarylamine arms has been synthesized and characterized. Self-assembled micrometric crystalline fibers can be formed in various organic solvents. This derivative has also been studied in chlorinated solvents upon visible light stimulation, giving rise to self-assembled fibers with triarylammonium cations trapped in their supramolecular structure. Overall, this work enlarges the scope of chemical modifications that can be made on triarylamine cores to produce doped supramolecular architectures with potential interests for optoelectronic materials.

An acid-base switchable [c2]daisy chain rotaxane terminated with two 2,6-diacetylamino pyridine units has been self-assembled with a bis(uracil) linker. The complementary hydrogen-bond recognition patterns, together with lateral van der Waals aggregations, result in the hierarchical formation of unidimensional supramolecular polymers associated in bundles of muscle-like fibers. Microscopic and scattering techniques reveal that the mesoscopic structure of these bundles depends on the extended or contracted states that the rotaxanes show within individual polymer chains. The observed local dynamics span over several length scales because of a combination of supramolecular and mechanical bonds. This work illustrates the possibility to modify the hierarchical mesoscopic structuring of large polymeric systems by the integrated actuation of individual molecular machines.

A family of triarylamine-fullerene conjugates has been synthesized and shown to self-assemble upon light stimulation in chlorinated solvents. This light-induced process primarily involves excitation of triarylamine derivatives, which then oxidize and stack with their neutral counterparts to form charge transfer complexes in the form of p-conducting channels, while fullerenes are consequently enforced in coaxial n-conducting columnar arrangements. These supramolecular heterojunctions can be organized over very long distances in micrometric fibers when a controlled amount of photons is provided from a white light source to initiate the process. Surprisingly, when sunlight or UV light is used instead, the nanostructuration leads to monodisperse spherical objects due to the nature of the nucleation-growth process involved in the stacks formation. This control over the supramolecular morphology of organic self-assemblies using the nature of light is of general interest for the design of functional responsive materials.

A logic gate based on a bistable [c2] daisy chain rotaxane decorated with lateral triarylamine units is described, giving rise to an INHIBIT logic function using proton concentration and light as inputs, and producing dual color change and supramolecular self-assembly as outputs.

International audience; The implementation of artificial molecular machines in polymer science is an important objective that challenges chemists and physicists in order to access an entirely new class of smart materials. To design such systems, the amplification of a mechanical actuation from the nanoscale up to a macroscopic response in the bulk material is a central issue. In this article we show that bistable [c2]daisy chain rotaxanes (i.e. molecular muscles) can be linked into mainchain Upy-based supramolecular polymers. We then reveal by an in depth quantitative study that the pH actuation of the mechanically active rotaxane at the nanoscale influences the physical reticulation of the polymer chains by changing the supramolecular behavior of the Upy units. This nano-actuation within the local structure of the main chain polymer results in a mechanically controlled sol-gel transition at the macroscopic level.

We have synthesized a series of triarylamine-cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by (1) H NMR and UV/Vis spectroscopy that their supramolecular self-assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable-temperature polarizing optical microscopy (VT-POM), variable-temperature X-ray diffraction (VT-XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar- or columnar-packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self-assemblies as electroactive materials from solution to mesophases.

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.

International audience; In this article, the dynamic structure of complex supramolecular polymers composed of bistable [c2]daisy chain rotaxanes as molecular machines that are linked by ureidopyrimidinones (Upy) as recognition moieties was studied. pH actuation of the integrated mechanically active rotaxanes controls the contraction/extension of the polymer chains as well as their physical reticulation. Small-angle neutron and X-ray scattering were used to study in-depth the nanostructure of the contracted and extended polymer aggregates in toluene solution. The supramolecular polymers comprising contracted nanomachines were found to be equilibrium polymers with a mass that is concentration dependent in dilute and semidilute regimes. Surprisingly, the extended polymers form a gel network with a crystal-like internal structure that is independent of concentration and reminiscent of a pearl-necklace network.

Supramolecular organic electronics rests on the use of bottom-up chemical self-assembly processes in order to design conducting components on the 5-100 nm scale. The challenges in this field are both the construction of 1D-nanostructures displaying optimized transport properties and their precise connections to electrodes. The present Research News highlights important advances in such materials regarding their electrical performances, from semiconductors to organic metals, but also regarding their processability. In particular, by externally controlling light-responsive supramolecular polymerization processes, and by using appropriate methods of casting with an applied electric field, it becomes possible to pre-determine the accurate positioning of organic interconnects within patterned nano-circuitry. These strategies using external stimuli to obtain addressability, thus hold promising alternatives to other conducting materials such as carbon nanotubes for further technological applications in nanosciences.

Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water.

International audience; Supramolecular self-assembly is a multiple length-scale and time-dependent process involving many coexisting components. Such complexity requires suitable strategies to extract quantitative dynamical and structural information on all involved species. Here, we detail an original light scattering method to study the kinetics of tailored triarylamine molecules capable of self-assembling in supramolecular highly conductive nanowires upon light exposure. These micrometric assemblies cause the emergence of intermittences in the scattered intensity and the construction of a predominant slow mode in the correlation function making separation between small-and large-size species impossible using conventional treatments. Our strategy is based on the time monitoring of intermittences and allows us to determine the fraction of nanowires as well as those of small critical nuclei and triarylamine building blocks as a function of time and light exposure, in good agreement with recent theoretical predictions.

We have investigated the self-assembly in water of molecules having a single hydrophobic bis-urea domain linked to different hydrophilic functional side chains, i.e., bioactive peptidic residues and fluorescent cyanine dyes. By using a combination of spectroscopy, scattering, and microscopy techniques, we show that each one of these molecules can individually produce well-defined nanostructures such as twisted ribbons, two-dimensional plates, or branched fibers. Interestingly, when these monomers of different functionalities are mixed in an equimolar ratio, supramolecular copolymers are preferred to narcissistic segregation. Radiation scattering and imaging techniques demonstrate that one of the molecular units dictates the formation of a preferential nanostructure, and optical spectroscopies reveal the alternated nature of the copolymerization process. This work illustrates how social self-sorting in H-bond supramolecular polymers can give straightforward access to multifunctional supramolecular copolymers.

Supramolecular organic electronics rests on the use of bottom-up chemical self-assembly phenomena in order to design conducting components on the 5–100 nm scale. The challenges to take up in this field are both the construction of 1D-nanostructures displaying optimized charge transport properties and their insertion in optoelectronic devices. This chapter describes the supramolecular structures and transport properties of various conducting self-assemblies based on the nature of their molecular constituents. In addition, it describes several processing strategies to engineer and integrate them in (opto)electronic devices such as field effect transistors, light emitting diodes, and organic solar cells. These functional materials open new doors for further fundamental investigations on charge transport phenomena and for technological applications in which bottom-up fabrication processes can overlap with pre-patterned top-down circuitries for improved miniaturization and efficiency.

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.

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.

In this review, we survey the diversity of structures and functions which are encountered in advanced self-assembled nanomaterials. We highlight their flourishing implementations in three active domains of applications: biomedical sciences, information technologies, and environmental sciences. Our main objective is to provide the reader with a concise and straightforward entry to this broad field by selecting the most recent and important research articles, supported by some more comprehensive reviews to introduce each topic. Overall, this compilation illustrates how, based on the rules of supramolecular chemistry, the bottom-up approach to design functional objects at the nanoscale is currently producing highly sophisticated materials oriented towards a growing number of applications with high societal impact.

Pumping iron: Double-threaded rotaxanes can be linked to coordination units and polymerized in the presence of iron or zinc ions. pH modulation triggers cooperative contractions (or extensions) of the individual rotaxanes, thus resulting in an amplified motion of the muscle-like supramolecular chains with changes of their contour lengths of several micrometers (see picture).

The dynamic processes in self-assemblies are involved in numerous domains that span throughout the modern aspects of chemical sciences, going from fundamental investigations into the origin of life to the most striking technological applications in medicine or electronics. This chapter aims at providing the reader with a brief overview of the concepts that link chemical reactivity with dynamic templates and catalysts made of large supramolecular assemblies. Specifically, we discuss kinetic and thermodynamic aspects of selected examples depending on (i) the nature of the matrix — that is, micelles, vesicles, liquid crystals, and gels; (ii) the nature of their constituents — that is, surfactants, block copolymers, bioactive macromolecules; and (iii) the nature of the chemical transformations that are performed — that is, reaction of small organic molecules, biomolecules, polymerizations, nanoparticle formation, and also reactions that involve the constituents of the matrix themselves as observed, for instance, in self-reproducing systems. In each section, we combine original papers that paved the field together with more recent works of particular interest; several reviews are also referenced to help in accessing a more comprehensive literature. Keywords: self-assembly; supramolecular chemistry; micelles; vesicles; surfactants; block copolymers; peptides; liquid crystals; gels; mesophases; nanostructuration; nanoreactors; materials synthesis; catalysis; polymerization; self-replication; dynamic combinatorial chemistry; chemical evolution

The dynamic processes in self-assemblies are involved in numerous domains that span throughout the modern aspects of chemical sciences, going from fundamental investigations into the origin of life to the most striking technological applications in medicine or electronics. This chapter aims at providing the reader with a brief overview of the concepts that link chemical reactivity with dynamic templates and catalysts made of large supramolecular assemblies. Specifically, we discuss kinetic and thermodynamic aspects of selected examples depending on (i) the nature of the matrix — that is, micelles, vesicles, liquid crystals, and gels; (ii) the nature of their constituents — that is, surfactants, block copolymers, bioactive macromolecules; and (iii) the nature of the chemical transformations that are performed — that is, reaction of small organic molecules, biomolecules, polymerizations, nanoparticle formation, and also reactions that involve the constituents of the matrix themselves as observed, for instance, in self-reproducing systems. In each section, we combine original papers that paved the field together with more recent works of particular interest; several reviews are also referenced to help in accessing a more comprehensive literature. Keywords: self-assembly; supramolecular chemistry; micelles; vesicles; surfactants; block copolymers; peptides; liquid crystals; gels; mesophases; nanostructuration; nanoreactors; materials synthesis; catalysis; polymerization; self-replication; dynamic combinatorial chemistry; chemical evolution

The structural and dynamical properties of dilute aqueous solutions of poly(ethylene glycol)-perylene diimides (PEG(n)-PDI) have been investigated by means of static and dynamic light scattering, TEM microscopy, and small-angle X-ray scattering experiments. The amphiphilic PEG(n)-PDI molecules first self-assemble into stable and compact primary stacks of a few units of planar PDI through hydrophobic and π-π interactions. These primary stacks subsequently arrange in large and globular aggregates of typically 100-250 nm via weak PEG chain interpenetration. Surprisingly, the scattered electric field autocorrelation function g((1))(q,t) measured by dynamic light scattering evolves over very long periods of times (several months) and up to a bimodal distribution. The fast relaxation mechanism is associated to the diffusion of free primary stacks, whereas the slower relaxation still indicates the presence of large self-assemblies. Kinetic experiments show that the large supramolecular aggregates slowly release the free primary stacks whose proportion increases with time. This dissociation depends on several parameters such as PEG side chain length, total concentration, and shaking.

International audience; Let there be more light: Triarylamine-based building blocks respond to visible-light exposure by the formation of cationic radicals that hierarchically self-assemble into molecular wires, which in turn combine within larger fibers (see picture). The stimuli-responsive supramolecular scaffold, which is created by charge transfer and reversibly broken up by heating, prevents the quenching of holes within the wires.