Complexes de métaux de transition organisés dans des nanostructures lamellaires hybrides fonctionnelles

Ce travail de thèse a permis d élaborer de nouveaux matériaux hybrides organiques inorganiques multifonctionnels. Nous avons montré qu il était possible selon un mécanisme d échange anionique de fonctionnaliser l espace interlamellaire de matériaux lamellaires de type Hydroxydes Simples Lamellaires par des complexes de métaux de transition (complexes de phthalocyanines, bases de Schiff métallées et complexes polypyridine de ruthénium). Grace à la mise au point d une méthode de synthèse par voie indirecte, nous avons pu nous affranchir des nombreuses difficultés liées à l insertion-greffage de ces complexes. L insertion de tels complexes a permis de préciser le mécanisme de mise en ordre magnétique de ces matériaux hybrides. L insertion d une phthalocyanine de cuivre permet ainsi de disposer d une sonde paramagnétique dans l espace interlamellaire et par là, d évaluer le champ interne résultant de la mise en ordre du matériau. Enfin, nous avons pu accéder à de nouveaux aimants multifonctionnels, associant par exemple magnétisme et chiralité ou magnétisme et luminescence.This PhD work allowed to elaborate new multifunctionnal inorganic/organic hybrid materials. We showed that it was possible to functionalize the interlayer space of Layered Simple Hydroxides by transition metal complexes (phthalocyanine complexes, Schiff bas complexes and ruthenium polypyridine complexes) via an anionic exchange mechanism. We thus developed a new synthetic procedure, called indirect synthesis . We have succeeded to overcome the numerous difficulties linked to the insertion grafting of coordination complexes. The insertion of such complexes allowed to precise the mechanism of the magnetic ordering of theses hybrid materials. The insertion of copper phthalocyanine allows to benefit from an internal paramagnetic probe in-between the inorganic layers, and thus to evaluate the internal field resulting from the magnetic ordering of the material. Finally, with this approach, we have been able to obtain new functional magnets, combining magnetism and chirality, or magnetism and luminescence.STRASBOURG-Sc. et Techniques (674822102) / SudocSudocFranceF

Electrocatalytic Properties of Metal Phthalocyanine Tetrasulfonate Intercalated in Metal Layered Simple Hydroxides (Metal: Co, Cu, and Zn).

International audienceA series of hybrid metal (Zn, Cu, and Co) layered simple hydroxides (LSH) functionalized by surfactants, namely, dodecylsulfonate (DS0) or dodecylsulfate (DS–) and by tetrasulfonato metal (Cu, Co)-phthalocyanines, was synthesized by anionic exchange reactions and characterized by ancillary techniques. The electrochemical properties of these compounds were investigated by cyclic voltammetry in phosphate buffer solutions over a wide potential range including that suitable for oxygen reduction. The electroactivity of intralayer metal cations (Cu and Co) was evidenced as a function of the phosphate buffer pH. The redox properties of Co- and Cu-PcTS0 grafted in LSH (Zn, Co, and Cu) were also investigated in neutral pH solution, under argon, air, or O2 atmospheres. Interestingly, these hybrid compounds display an electrocatalytic behavior toward the reduction of oxygen. In particular with CoPcTS0-LSH, a sharp electrocatalytic reduction wave is observed at −0.40 V/Ag-AgCl with an intensity that depends on the oxygen concentration. The formation of a CoPc-O2 grafted species in the presence of oxygen was confirmed by electron paramagnetic resonance spectroscopy