title: 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.
authors.affiliation: Sorbonne Universités, UPMC Université Paris 06, CNRS UMR 8232, Institut Parisien de Chimie Moléculaire, Université Pierre et Marie Curie , 4 Place Jussieu, F-75005 Paris, France.
authors.forename: Guillaume
authors.initials: G
authors.lastname: Izzet
authors.affiliation: Laboratoire de Physique des Solides, Université Paris-Sud , CNRS UMR 8502, 91405 Cedex Orsay, France.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Abécassis
authors.affiliation: Sorbonne Universités, UPMC Université Paris 06, CNRS UMR 7197, Laboratoire de Réactivité de Surface, Université Pierre et Marie Curie , 4 Place Jussieu, F-75005 Paris, France.
authors.forename: Dalil
authors.initials: D
authors.lastname: Brouri
authors.affiliation: Sorbonne Universités, UPMC Université Paris 06, CNRS UMR 8232, Institut Parisien de Chimie Moléculaire, Université Pierre et Marie Curie , 4 Place Jussieu, F-75005 Paris, France.
authors.forename: Madeleine
authors.initials: M
authors.lastname: Piot
authors.affiliation: Sorbonne Universités, UPMC Université Paris 06, CNRS UMR 8232, Institut Parisien de Chimie Moléculaire, Université Pierre et Marie Curie , 4 Place Jussieu, F-75005 Paris, France.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Matt
authors.affiliation: Catalan Institute of Chemical Research (ICIQ), The Barcelona Institute of Science and Technology , Avinguda dels Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Stefano Artin
authors.initials: SA
authors.lastname: Serapian
authors.affiliation: Catalan Institute of Chemical Research (ICIQ), The Barcelona Institute of Science and Technology , Avinguda dels Països Catalans 16, 43007 Tarragona, Spain.|Departament de Química Física i Inorgànica, Universitat Rovira i Virgili , Avinguda dels Països Catalans, 26, 43007 Tarragona, Spain.
authors.forename: Carles
authors.initials: C
authors.lastname: Bo
authors.affiliation: Sorbonne Universités, UPMC Université Paris 06, CNRS UMR 8232, Institut Parisien de Chimie Moléculaire, Université Pierre et Marie Curie , 4 Place Jussieu, F-75005 Paris, France.
authors.forename: Anna
authors.initials: A
authors.lastname: Proust