2026-04-18T02:59:27Zhttps://recercat.cat/oai/request

oai:recercat.cat:2072/3057402026-01-15T14:12:34Zcom_2072_300912com_2072_4427col_2072_301309

Hierarchical Self-Assembly of Polyoxometalate-Based Hybrids Driven by Metal Coordination and Electrostatic Interactions: From Discrete Supramolecular Izzet, Guillaume Abécassis, Benjamin Brouri, Dalil Piot, Madeleine Matt, Benjamin Serapian, Stefano Artin Bo, Carles Proust, Anna DFT selfassemby POMs polyoxometalates hybrids <p> 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 <em>ca.</em> 50 POMs that were characterized by SAXS and High-Resolution Transmission Electron Microscopy (HR-TEM). This multi-scale 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.</p> 2016 info:eu-repo/semantics/article http://hdl.handle.net/2072/305740 https://doi.org/10.1021/jacs.6b00972 eng MINECO I+D+I Severo Ochoa Excellence Accreditation 2014–2018 J Am Chem Soc CTQ2014-52824-R SEV-2013-0319 info:eu-repo/semantics/openAccess application/pdf American Chemical Society RECERCAT (Dipòsit de la Recerca de Catalunya)