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The EPR double integrations allowed us to evaluate the quantity of mononuclear Cu(II) (spin 1/2) by comparing it with the EPR response in the same solvent and same temperature of the parent dicationic complex (1, same quantity in the same volume).
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39
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See refs 16 and 27
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The geometry of the mononuclear complex, as proposed in Scheme 1, is quite similar to that obtained with Cu(II) and a calixarene-based ligand presenting a phenolate group covalently bound to one of the nitrogenous arm: Sénèque, O.; Campion, M.; Douziech, B.; Giorgi, M.; Le Mest, Y.; Reinaud, O. J. Chem. Soc., Dalton Trans. 2003, 4216-4218. Simple modeling (Dreiding or ChemBats3D) indicates overcongestion around the metal center because of steric interactions with the calixarene core and the methoxy substituents for a hypothetical structure involving simultaneously (i) endo binding of an imidazole and (ii) exo binding of the two other imidazolse + OH + guest. In the dinuclear structure, the Cu(II) ions are bound in the exo position to two imidazole arms belonging to two different calixarenes, which allows for relative steric decongestion. Such a steric constraint due to the macrocycle actually leads to the formation of tri- and tetranuclear species in the presence of extra copper and anions. See refs 16 and 27.
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31044431603
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Complex 3 could not be isolated as a pure compound; indeed, it is stable only in the presence of excess acetamide. Otherwise, it evolves toward multinuclear acetato-Cu(II) complexes.
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