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Synthèse et étude physico-chimique de ligands macrocycliques, macrobicycliques et macrotricycliques dérivés du 5,12-dioxocyclame

Abstract : The synthesis and the physico-chemical studies of macropolycyclic ligands based on 5,12-dioxocyclam L1 are presented. The first part of this dissertation presents the structural and physico-chemical properties of L1 and its N-substituted derivatives L2 and L3. A potentiometric study reveald a cooperative protonation of the two macrocyclic ligands L1 and L2 whereas the study of the macrotricycle L3 in a methanol-water mixture revealed a sequential cooperative diprotonation of the four tertiary amines. The square planar nickel and copper complexes were synthesized and characterized using infrared, UV-vis and ESR spectgroscopy. The spectroscopic studies showed the presence of intermolecular hydrogen bonds between the amidic oxygen and the crystallized water molecules that affect the energy levels of the copper d orbitals. The second part of this manuscript is focused on the synthesis and the physico-chemical properties of ansa-bridged ligands (L4, L5, L6 and L7). The structural and spectroscopic studies of the free macrobicycles L4, L5 and L6 revealed the presence of intramolecular hydrogen bonds involving the tertiary amines lone pairs. The copper(II) complexes derived from these ligands have been characterized by X-ray cristallography and by infrared, UV-vis and ESR spectroscopy. Distorted square planar complexes have been obtained from the tetradentate ligands L4 and L5. The pentadentate ligand L6 is able to form two well-defined complexes, a red one and a blue one, depending on the pH. Finally, the copper(II) complex [Cu(L7)](ClO4) has been characterized by X-ray crystallography. The structure shows a short Cu(II)--arene bond as well as a distortion of the aromatic ring.
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Laurent Fremond. Synthèse et étude physico-chimique de ligands macrocycliques, macrobicycliques et macrotricycliques dérivés du 5,12-dioxocyclame. Chimie. Université de Bourgogne, 2002. Français. ⟨tel-00268740⟩

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