Multifunctional Supramolecular Gels with Strong Mechanical Properties Formed by Self-Assembly of Polyoxometalate-Based Coordination Polymers
Résumé
Metallogels built in a bottom-up approach by metal coordination and supramolecular interactions have important potential for the elaboration of smart materials. In this context, we present here the formation of supramolecular coordination polymers driven by the complexation of cobalt(II) or zinc(II) ions with polyoxometalate-based hybrids displaying two terpyridine ligands in a linear arrangement. Thanks to the electrostatic interactions between the polyoxometalate cores and metal nodes, the polymer chains selfassemble into fibers that physically cross-link to form gels above a critical concentration. Using spectroscopy, microscopy, X-ray scattering, and rheometry, complemented by molecular dynamics simulations, we investigated the supramolecular organization of the chains in the fibers and the resulting processes leading to gelation. Compared to previously reported systems, these gels have improved rheological features and appealing properties, such as birefringence, luminescence, and spin crossover, paving the way for their use as building blocks for multifunctional smart materials.
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