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<dc:title xml:lang="en">Synthesis, characterization and photochemical properties of 3d transition metal supported by aroyl-hydrazone ligands</dc:title>
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<dc:subject xml:lang="fr">Photoréduction</dc:subject>
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<dcterms:abstract xml:lang="fr">Ce travail de thèse explorait certains aspects de la chimie de coordination de complexes moléculaires à bases de métaux 3d (Fe, Cu, Mn et Ni) supportés par des ligands azotés de type aroyle-hydrazone. Le travail de cette thèse était plus particulièrement centré sur le développement des nouveaux ligands et la photo chimie des complexes ferriques, afin d’élucider en particulier les mécanismes de la photo réduction qui valorise un brevet du laboratoire sur la production et le stockage d’énergie solaire via la photo réduction d’ions ferriques. Les complexes mis en jeu dans le processus ont été totalement caractérisés en solution et à l’état solide. Ce phénomène prend place en solution comme en solution gelée. La cinétique du processus photochimique a été suivie par UV-Visible comme par RPE. Cette photo réduction passe par un intermédiaire radicalaire et le solvant joue le rôle du donneur des électrons. Ce processus a été totalement étudié : l’effet du solvant, l’effet de la modification dans la sphère de coordination du complexe, l’effet de la modification de la périphérie des ligands et finalement l’effet des longueurs d’ondes. D’autres domaines sont également explorés, comme le magnétisme moléculaire ou encore la catalyse homogène (oligomérisation de l’éthylène) avec des complexes à base de Ni2+.</dcterms:abstract>
<dcterms:abstract xml:lang="en">This PhD thesis explored some aspects of the coordination chemistry of molecular complexes based on 3d transition metal ions (Fe, Cu, Mn and Ni) coordinated by multidentate aroyl-hydrazone ligands. The work of this thesis was particularly focused on the development of new ligands, their coordination chemistry and the photochemistry of ferric complexes. The central objective of this work was to elucidate the mechanism of the photo reduction process, in order to valorize an already accepted laboratory patent on the production and storage of solar energy. The complexes involved in the process have been fully characterized in solution and in the solid state. This phenomenon takes place in solution as in frozen solution. The kinetics of the photochemical process was followed by UV-Visible as by RPE. This photo reduction passes through a radical intermediate and the solvent plays the role of the electron donor. This process has been fully studied: the effect of the solvent, the effect of the modification in the coordination sphere of the complex, the effect of the modification of the periphery of the ligands and finally the effect of the light and different wavelengths. Other fields are also explored, such as molecular magnetism for different mono and dinuclear iron and manganese complexes or even homogeneous catalysis (oligomerization of ethylene) with complexes based on Ni(II).</dcterms:abstract>
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