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Synthèse de nouveaux ligands tridentates : préparation et étude physico-chimique des complexes de Ruthénium (II) correspondants

Abstract : Ruthenium(II) complexes present rich photophysical properties and so constitute good candidates in the systems of catching of light energy. They notably allow the photosensitization of TiO2 in the Graetzel solar cells. In this context, various Ruthenium(II) complexes containing oligopyridinic tridentates ligands were prepared and their physicochemical properties studied. In binuclear complexes, it was shown that cyclometalation associated to a weak intermetal distance allows to improve the electronic communication between these two metal centres. The cyclometalation has also been studied in a mononuclear complex bearing a carboxylic group, allowing the anchoring to TiO2 ; this complex was tested in a solar cell and its efficiency of photovoltaic conversion mesured. On the other hand, with the aim of an use in a quite solid solar cells, complexes bearing thienyl groups were synthetized, polymerized and studied. In the complexes containing a polythiophene directly connected to the terpyridine moiety, the excited electron, further to absorption of a photon, is localized on the thienyl group which traps then the electron and prevents its good injection in the conduction band of TiO2. In our study, we introduced a spaceur between these two moities ; it was shown that the electron is not then localized any more on the thiophene, what lets augur an effective injection of this one in the semiconductor. Ruthenium(II) complexes also constitute electrochemical sensors due to the redox character of the transition metal. This application is the object of the second part of the work presented in this report. Terpyridine complexes bearing a quinone function were so prepared with the aim of a chemical detection of glutathione. The addition of the glutathione on these complexes was revealing as well as the modification then engendered by the electrochemical signal.
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Stéphanie Etienne. Synthèse de nouveaux ligands tridentates : préparation et étude physico-chimique des complexes de Ruthénium (II) correspondants. Autre. Université Paul Verlaine - Metz, 2005. Français. ⟨NNT : 2005METZ022S⟩. ⟨tel-01752382⟩

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