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.

C 3 -Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups,u ndergo supramolecular polymerization and further gelation by p-p stacking and hydrogen bondingoftheir TATA cores.B yusing subsequentr ing-opening metathesisp olymerization, these physical gels are permanently crosslinked into chemical gels. Detailedc omparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by opticals pectroscopies, electronic spectroscop-ies, atomicf orce microscopy,e lectronic paramagnetic resonance spectroscopy,X -ray scattering, electronic transport measurements, and rheology.T he resultsp resented here clearlye vidence that the core structure of the functional supramolecular polymers can be precisely retained during the covalentc apturew hereas the mechanical properties of the gels are concomitantly improved, with an increaseo f their storagemodulusb yt wo orders of magnitude.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

Supramolecular nanowiring is based on the precise interconnection of nano-or microelectronic circuit elements with electroactive supramolecular polymers displaying directional charge transport properties. It is a particularly attractive topic of current research in order to access miniaturized organic electronic devices. The bottom-up construction of such integrated nanowires can be generated by specific supramolecular polymerization processes -based on addressed nucleation growth mechanisms -which provide a spatial precision in their placement that cannot be accessed by top-down approaches. However, to implement, quantify, and validate such 2 supramolecular interconnects in nanotechnologies, powerful characterization techniques, which probe both the fine structural and orientational features of the nanowires, are still required. Most techniques usually lack the ability to access the morphological parameters of the targeted nanostructures lodged within the electronic circuits at that scale (for instance between micro/nanoelectrodes). Even grazing-incidence wide-angle X-ray scattering (GIWAXS) poses major hurdles for the practical investigation of such miniaturized electronic devices due to beam path obstruction for most in-plane orientation of the samples. To overcome these limitations, we have implemented a sensing modality based on GIWAXS collection for unique sample orientation and spot shape analysis in reciprocal space allowing the entire film morphology to be accessed. In this case study involving triarylamine-based nanowires, we fully determine in a single experiment the packing structure of the supramolecular polymers interconnecting microelectrodes, together with their 3D and 2D orientational order parameters (S3D ≈ 0.986 and S2D ≈ 0.91). Our investigation demonstrates that the nanowires lie not only flat along the substrate but are also aligned along the normal to the electrodes. Furthermore, this alignment occurs with a coherent length of more than 100 nm, representing more than 200 molecular lengths along the nanowire axis. From a broader perspective, this work highlights the high potential of GIWAXS to become a reference method for achieving the full characterization of nanowiring processes with various types of supramolecular polymers and polymer self-assemblies integrated in complex device geometries.