Skip to Main content Skip to Navigation

Design of polymetallic uranium assemblies for the development of single molecule magnets

Abstract : The study of actinide chemistry is not only essential for the development of nuclear fuel, nuclear fuel reprocessing or environmental clean up, but also for the understanding of fundamental actinide/ligand interactions and multiple bounding. The magnetic properties of polynuclear actinide molecules are of significant interest to investigate the magnetic communication between the metallic centres. Furthermore, they are highly promising for the design of molecular magnets. Uranium undergoes redox reactions due to a wide range of available oxidation states and easily forms polynuclear assemblies. However, only a few controlled synthetic routes towards these polynuclear uranium assemblies are described in the literature. In this context, the first part of this work was dedicated to the synthesis of oxo/hydroxo uranium clusters from the controlled hydrolysis of tetravalent uranium in the presence of an environmentally relevant ligand. This led to the synthesis of clusters with novel topologies, for which size could be varied as a function of the reaction conditions employed. However, the obtained clusters do not behave as SMM. In order to gain a stronger interaction between metallic centres, the cation-cation interaction was used to rationally design polynuclear uranyl(V) complexes. The isolation of uranyl(V) complexes had been limited in the past by its disproportionation, however, a fine tuning of the organic ligand and reaction conditions finally allowed to stabilise uranyl(V). We used stable uranyl(V) units as building block to form heteronuclear complexes with 3d and 4f metals with polymeric or discrete structures. The study of the magnetic properties of the uranium polynuclear assemblies was carried out and revealed single molecule or chain magnet behaviours with high energy barriers. The uranyl(V) unit was also used as a structural model for the more radioactive neptunium element, allowing the isolation of an isostructural trinuclear neptunyl(V) assembly in similar reaction conditions. Finally, the use of a nitride ligand as a bridging unit, allowing the formation of uranium-ligand multiple bonds, was explored to build novel di-uranium complexes supported by siloxy ligands. Nitride molecules containing unprecedented uranium in the +III oxidation state were isolated and characterised.
Document type :
Complete list of metadata
Contributor : ABES STAR :  Contact
Submitted on : Tuesday, January 16, 2018 - 2:38:10 PM
Last modification on : Friday, March 25, 2022 - 9:44:32 AM


Version validated by the jury (STAR)


  • HAL Id : tel-01685504, version 1



Lucile Chatelain. Design of polymetallic uranium assemblies for the development of single molecule magnets. Inorganic chemistry. Université Grenoble Alpes, 2016. English. ⟨NNT : 2016GREAV076⟩. ⟨tel-01685504⟩



Record views


Files downloads