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Matériaux moléculaires à base de lanthanides et de métaux de transition : de la synthèse à l’architecture cristalline

Abstract : New tridimensional 4f-3d molecular materials can be obtained through crystal growth in gel medium. A simple, economic, ecologic and environmentally friendly synthesis method that has been used until recently for the growth of mononuclear crystalline molecular materials. During this international joint PhD between Assane Seck Ziguinchor University (Senegal) and Lorraine University (France), it was possible to synthesize several novel crystalline phases of molecular materials. Ten new 4f-3d heteronuclear molecular materials was obtained by slow diffusion in gel medium and structurally characterized by single crystal X-ray diffraction. Eight of them belong to the same family of isostructural compounds [Ln(III)M(II)(3,5-pdc)2(Oxa)0.5(H2O)8]2H2O (Ln = Pr, Nd, Sm, Eu, Gd and M = Cu, Co) and can be described as one-dimensional coordination polymers. Their structure is composed of dinuclear chains sandwiching oxalate ligands and the three-dimensional network is ensured by hydrogen bonds of water molecules assisted by π-π* stacking interactions. The last two are three-dimensional coordination polymers. The one based on Sm3+ and Cu2+ [SmCu(3,5-pdc)2(Oxa)0.5(H2O)6]2H2O is a polymorph to a compound belonging to the family of isostructural compounds. Its structure consists of parallel layers bridged by oxalate ligands to generate a final three-dimensional network. As for the compound based on Dy3+ and Ni2+ [DyNi0.5(3,5-pdc)0.5(Oxa)1.5(H2O)3,5]6,5H2O it is a Metal-Organic Framework (MOFs). Its structure is formed of honeycomb layers constructed with three types of oxalate ligand interconnected by the core ligand pyridine-3,5-dicarboxylate to give rise to a porous three-dimensional structure.
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Mamoudou Diallo. Matériaux moléculaires à base de lanthanides et de métaux de transition : de la synthèse à l’architecture cristalline. Chimie. Université de Lorraine; Université Assane Seck (Ziguinchor, Sénégal), 2020. Français. ⟨NNT : 2020LORR0010⟩. ⟨tel-02863301⟩

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