Metal Cyclen supramolecular entities tailored by the bridging effect of counter anions as potential separator for energy storage systems

Nowadays, supramolecular entities as covalent organic framework, metal-organic framework or even supramolecular polymers have emerged as an extensive class of materials for their broad application and properties. Herein, from a relatively simple and original chemistry, we have developed an organic-inorganic fibers by a spontaneous self-assembly process. Indeed, we design one ligand starting from 1,4,7,10-tetraazacyclododecane which, associated with metallic salts, allows the development of fibers by self-assemblies called TSC@MX 2 (TSC for tetrastyrylcyclen, MX 2 = metal salt used). The process was also studied with tetrabenzylcyclen (TBC) ligand to demonstrate how the terminal group as styryl (in the case of TSC) is important. We therefore plan in a first step to study the influence of various counterions as well as the possibility of extending this approach to other transition metals, from different families and periods. Here, we further presented the synthesis of metallo-cyclen derivatives-based fibers and reported their application as a first approach towards fully organic separators due to their intertwined nature for an electric double layer capacitor system. These electrochemical tests clearly highlighted the potential of TSC-based material as separator for energy storage systems as they can be used in both organic and aqueous environments. • The spontaneous formation of organic–inorganic fibres occurs through the self-assembly of metallo-cyclen derivatives. • Novel TSC@MX 2 materials have been developed based on a simple and original ligand design. • Styryl functionalization has been shown to be crucial for fibre formation, compared to benzyl analogues. • TSC fibres show promising electrochemical performance as separators for energy storage in organic and aqueous media.