Synthèse d’assemblages multimétalliques de lanthanides : des propriétés électroniques des précurseurs divalents au contrôle de leur réactivité

Abstract : Divalent lanthanide chemistry has long been hampered by the lack of adapted precursors. This work is therefore focussing on the preparation of new divalent lanthanides precursors and their use in small molecule activation for building new materials.Triflate precursors were prepared and their solution properties were studied. ith their multiple coordination modes, triflate anions were shown to favour assemblies growth.Another type of precursor was also prepared: the lanthanidocene. Although organometallic chemistry of lanthanide is often known for the poor control of the complexes symmetry, a 9-membered ligand allowed the preparation of the "true" divalent ytterbocene and samarocene.The electronic properties of divalent lanthanides complexes are poorly known. The prepared thulium (II) precursors were therefore extensively studied. The influence of the symmetry on electronic properties was caracterised and a well-chosen set of ligands was proven to enable interesting magnetic properties such as single-molecule-magnet behaviour.The last part of this work focused on the reactivity of these precursors towards small molecules. Assemblies were grown from the reactivity of divalent samarium with carbon dioxide or yellow sulfur. On one of the obtained assemblies, supramolecular chemistry was carried out, progressively bridging the gap between molecules and materials.
Complete list of metadatas

Cited literature [598 references]  Display  Hide  Download

https://pastel.archives-ouvertes.fr/tel-02265243
Contributor : Abes Star <>
Submitted on : Friday, August 9, 2019 - 1:01:23 AM
Last modification on : Sunday, August 11, 2019 - 1:09:37 AM

File

69851_XEMARD_2018_archivage.pd...
Version validated by the jury (STAR)

Identifiers

  • HAL Id : tel-02265243, version 1

Citation

Mathieu Xemard. Synthèse d’assemblages multimétalliques de lanthanides : des propriétés électroniques des précurseurs divalents au contrôle de leur réactivité. Chimie inorganique. Université Paris-Saclay, 2018. Français. ⟨NNT : 2018SACLX055⟩. ⟨tel-02265243⟩

Share

Metrics

Record views

372

Files downloads

25