Hierarchical Self-Assembly of Polyoxometalate-Based Hybrids Driven by Metal Coordination and Electrostatic Interactions: From Discrete Supramolecular Species to Dense Monodisperse Nanoparticles

Abstract : The metal-driven self-assembly processes of a covalent polyoxometalate (POM)-based hybrid bearing remote terpyridine binding sites have been investigated. In a strongly dissociating solvent, a discrete metallomacrocycle, described as a molecular triangle, is formed and characterized by 2D diffusion NMR spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and molecular modeling. In a less dissociating solvent, the primary supramolecular structure, combining negatively charged POMs and cationic metal linkers, further self-assemble through intermolecular electrostatic interactions in a reversible process. The resulting hierarchical assemblies are dense monodisperse nanoparticles composed of ca. 50 POMs that were characterized by SAXS and transmission electron microscopy (TEM). This multiscale organized system directed by metal coordination and electrostatic interactions constitutes a promising step for the future design of POM self-assemblies with controllable structure-directing factors.
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Journal of the American Chemical Society, American Chemical Society, 2016, 138 (15), pp.5093 - 5099. 〈10.1021/jacs.6b00972〉
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https://hal.sorbonne-universite.fr/hal-01548125
Contributeur : Isabelle Vuillaume <>
Soumis le : mardi 27 juin 2017 - 11:16:06
Dernière modification le : mercredi 21 mars 2018 - 18:57:54

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Guillaume Izzet, Benjamin Abécassis, Dalil Brouri, Madeleine Piot, Benjamin Matt, et al.. Hierarchical Self-Assembly of Polyoxometalate-Based Hybrids Driven by Metal Coordination and Electrostatic Interactions: From Discrete Supramolecular Species to Dense Monodisperse Nanoparticles. Journal of the American Chemical Society, American Chemical Society, 2016, 138 (15), pp.5093 - 5099. 〈10.1021/jacs.6b00972〉. 〈hal-01548125〉

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