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Synthesis and characterization of dinuclear {Fe(μ-CN)Co} complexes exhibiting metal-to-metal electron transfer properties

Abstract : This thesis is dedicated to the synthesis of new dinuclear cyanido-bridged Co/Fe complexes, which mimics on a single molecule the original properties of the coordination network of Prussian Blue Analogues AxCo[Fe(CN)6]y•nH2O (A= alkaline ions), i.e. intramolecular thermal and photo-induced electron transfer in the solid state. We focus on the study of the physical properties of the simplest Fe/Co PBA, a dinuclear complex, with the hope to understand the fundamental concepts of this fascinating phenomenon. Chapter I contains the most representative examples of Fe/Co PBAs, focusing on the synthetic strategies employed in order to obtain Fe/Co PBAs of different dimensionalities and the techniques used to understand their photomagnetic properties. The theoretical background of the electron transfer phenomenon and the motivation of our work are described in the end of the chapter. After introducing the choice of the building blocks used in this work through the study of their redox potential properties, chapter II is devoted to the synthesis and the characterization of a novel dinuclear Fe/Co cyanido-bridged complex, which exhibits metal-to-metal electron transfer properties in solid state triggered by temperature and light. The ET phenomenon has been also studied by X-ray absorption spectroscopy and dielectric measurements. In Chapter III is illustrated the influence of the environment content of the dinuclear Fe/Co complexes, such as the counter ions, on the occurrence of the thermally and/or photo-induced electron transfer in solid state, thus highlighting the versatility of these molecular materials. Finally in chapter IV, the possibility of transferring the electron transfer phenomenon of the studied Fe/Co pairs from solid state to solution is investigated.
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Submitted on : Thursday, December 7, 2017 - 10:17:30 AM
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Evangelia S. Koumousi. Synthesis and characterization of dinuclear {Fe(μ-CN)Co} complexes exhibiting metal-to-metal electron transfer properties. Chemical Physics [physics.chem-ph]. Université de Bordeaux, 2015. English. ⟨NNT : 2015BORD0306⟩. ⟨tel-01655504⟩



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