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.

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.

Gaining control over supramolecular polymerization mechanisms is of high fundamental interest to understand self-assembly and self-organization processes at the nanoscale.Itisalso 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.T he involved mechanism offers new opportunities to precisely address in space and time the nucleation of supramolecular polymers at an electrode.T oi llustrate the potential of this methodology,s upramolecular nanowires are grown an oriented over several tens of micrometers between different types of commercially available electrodes submitted to asingle DC electric field, reaching ap recision unprecedented in the literature.

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.

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 C unit increases the dimensionality of the self-assembly process by reticulating the 1D nanowires typically obtained from the supramolecular polymerization of triarylamine monomers.

Zinc/bromine flow batteries are a promising solution for utility-scale electrical energy storage. The behavior of complex Zn–halogen species in the electrolyte during charge and discharge is currently not well-understood, and is an important aspect to be addressed in order to facilitate future electrolyte formulations. The speciation of the primary zinc bromide electrolyte with and without a secondary zinc chloride electrolyte is studied in the present work. Raman spectroscopy was carried out on aqueous solutions of zinc bromide at 5 concentrations (2–4 M) to account for the initial and later stages of charging, with 3 concentrations (1–2 M) of zinc chloride. Mixed solutions containing various combinations of each primary and secondary electrolyte concentrations were also studied. Semi-quantitative analysis of peaks after Gaussian and Lorentzian peak deconvolution showed that the proportion of four-ligand coordinated Zn–halides (i.e. [ZnBr4]2− and [ZnCl4]2−) increases with higher salt concentration, as compared to complexes with lower halide coordination numbers. The presence of a previously unassigned peak was observed at the 220 cm−1 band in the Raman spectra of mixed electrolytes. Results from ab-initio molecular modeling using the GAUSSIAN 16 software package suggests this peak is due to the presence of the hybrid-halide anionic complex [ZnBr2Cl(H2O)]–. Increasing the Cl:Br ratio in electrolytes promotes hybridization and subsequently decreasing the proportion of single-halide Zn–Br complexes. While this speciation study is focused on Zn/Br batteries, the findings are also potentially applicable to other energy storage and electrochemical systems containing zinc halide electrolytes.

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The full extent to which the electrochemical properties of MoS 2 electrodes are influenced by their morphological characteristics, such as crystalline disorder, remains unclear. Here, we report that disorder introduced by ball-milling decreases the Faradaic component of cell capacity and leads to increasingly pseudo-capacitive behaviour. After high temperature annealing, a more battery-like character of the cell is restored, consistent with a decrease in disorder. These findings aid the optimisation of MoS 2 electrodes, which show promise in several battery technologies.