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Mise en forme et étude des propriétés de complexes photo et redox actifs confinés dans des couches minces de silice organisées et orientées verticalement

Abstract : This thesis deals with the optimal immobilization and study of the properties of spin transition complexes in vertically aligned silica thin films. Such films are obtained by the electrochemically assisted self-assembly (EASA) method. The aim of this work is to develop hybrid organic-inorganic silica-based nanocomposites, in which coordination complexes are confined, which are both redox and photo active that is whose physical properties are controlled by light irradiation or by the application of a potential. To achieve this goal, we have followed different confinement approaches, notably: the one pot encapsulation, impregnation in silica films already synthesized (unmodified or functionalized with sulfonate groups), and finally combining the EASA method with click chemistry. As prototype of complexes, we chose [Fe(Htrz)3]2+, which is a one-dimensional polymer, and the mononuclear complex [Fe(bpy)3]2+ The research carried out has evidenced the role played by the polymeric structure of the [Fe(Htrz)3]2+ complex in the formation of the film, and its influence on the mesostructure when following the one-pot encapsulation method. Moreover, it has been possible to elucidate the role of counter anion, in particular that of sulfonate groups, in the complexation process, as well as the various factors involved in the spin transition within the nanocomposites. The manuscript ends with the study of photo induced spin crossover properties in the [Fe(bpy)3]2+ complex immobilized by covalent bonds in silica films.
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Samuel Ahoulou. Mise en forme et étude des propriétés de complexes photo et redox actifs confinés dans des couches minces de silice organisées et orientées verticalement. Matériaux. Université de Lorraine, 2019. Français. ⟨NNT : 2019LORR0243⟩. ⟨tel-02555848⟩

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