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Soutenance de thèse de Madame Suchithra ASHOKA SAHADEVAN

10h00 | Università degli Studi di Cagliari | ITALY

Sujet : Anilate-based Molecular Building Blocks for Metal-Organic Frameworks and Molecular Conductors

Directeur de thèse : Monsieur Narcis AVARVARI


This work reports on the design, synthesis and characterization of novel anilate-based functional/multifunctional molecular materials showing luminescent, magnetic and/or conducting properties. The family of anilate ligands comprises several derivatives obtained by introducing various substituents (H, F, Cl, Br, I, CN, etc.) at the 3 and 6 positions of the common 2,5-dihydroxy-1,4-benzoquinone framework. Among the anilate ligands, the only known  heterosubstituted chlorocyanilate ligand, ClCNAn2-, have been selected for preparing a novel family of 2D layered Coordination Polymers (CPs) with both 3d metal ions and 4f lanthanide ions, through a general and straightforward synthetic strategy. The materials obtained can be summarized as follows: (i) Mixed-valence multifunctional FeIIFeIII 2D CPs formulated as [TAG][FeIIFeIII(ClCNAn)3], (ii) 2D CPs based on NIR-emitting lanthanides and ClCNAn2-. These layered compounds were also exfoliated to nanosheets, by a top-down strategy involving sonication-assisted solution synthesis, time-resolved photoluminescence studies were also performed on both the bulk and nanosheets, (iii) Novel family of heteroleptic 2D CPs based on NIR-emitting lanthanides, ClCNAn2- and carboxylate derivative ligands, (iv) Novel family of 2DCPs based on DyIII and ClCNAn2- were prepared in order to investigate their magnetic properties. (v) Furthermore, the ability of the anilate ligands to work as components of BEDT-TTF- based molecular conductors has been demonstrated through the synthesis, via electrocrystallization technique, (vi) П-d hybrid multifunctional paramagnetic molecular conductors obtained by combining BEDT-TTF and [Fe(ClCNAn)3]3- as conducting and magnetic carrier respectively are also reported.

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