Multi-redox porous crystalline hybrid chalcogenides
French National Research Agency (ANR)
Funder: French National Research Agency (ANR)Project code: ANR-19-CE08-0029
Funder Contribution: 553,642 EUR
While zeolites or Metal-Organic Frameworks (MOFs) are suitable in numerous fields involving adsorption-desorption processes, their poor electronic conductivity, associated to the nature of the constitutive bonds involving the very electronegative oxygen, is a noticeable drawback in every application involving electron transfer. This project thus aims at bridging the gap between such insulating, porous materials and dense inorganic conductors, by focusing on the preparation and in-depth characterization of new crystalline hybrid organic-inorganic chalcogenides, with the final aim at combining in the designed solids porosity, electronic conductivity and multi-redox (cationic/inorganic and anionic/organic) activity. Our strategy relies on the use of sulfur-based, 1,2-dithiolene type ligands. With their fully delocalized frontier orbitals, three accessible redox states and ability to form stable complexes with both 3d and 4d metal ions, they can be considered as ideal non innocent ligands (meaning that at least one frontier orbital of the derived complex involves both the cation and the p system of the ligand). This leads to unique electronic properties and complex electrochemical behaviors in solution, but such properties have been scarcely exploited in extended solids yet. Synthesis, structure resolution and physico-chemical studies of new coordination networks will then be the core of the project. It relies on the combination of (i) innovative synthetic strategies, (ii) the thorough determination of the crystal structures by a combination of advanced diffraction methods and spectroscopies, (ii) the in-depth investigation of the electronic properties by a combination of experimental and computational tools. Finally, the performance of these solids as electrode materials for ion-batteries and hydrogen evolution reaction (HER) will be evaluated, anticipating that their characteristics allow overcoming some limitations of O-based MOFs and inorganic sulfides for such applications.
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