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A new series of ligands, containing one (L1H(2)-L4H(2)) or two (L5H(4)-L6H(4)) 1,4,8,11-tetraaza-5,7-dione units and functionalized with a propargyl group on the C atom between the C=O moieties, has been synthesized. Protonation constants for the ligands and formation constants of their Cu(2+) complexes have been determined in water, and the coordination geometry of the complexes existing at various pH values has been investigated by coupled pH-metric and spectrophotometric titrations. Ligands capable of simple uptake of Cu(2+) with the formation of neutral, square-planar complexes containing the -2-charged diamino-diimido donor sets and ligands containing further coordinating groups (quinoline or pyridine) capable of single and double cation translocation have been investigated. The role of the substituents on the amino groups and the structural role played by the propargyl group have been examined as regards Cu(2+) complexation and translocation. In the double-translocating ligand L6H(4), when the two Cu(2+) ions move inside the diamino-diamido donor set, the slim propargyl group allows an unprecedented folding of the whole ligand with apical coordination of one pyridine to form a five-coordinate, square-pyramidal Cu(2+) ion. The crystal and molecular structures of this unusual [L6Cu(2)] complex have been determined by X-ray diffraction. Finally, oxidation of Cu(2+) to Cu(3+) has been studied by cyclic voltammetry in water, which revealed that the redox reaction occurs only when the copper cation is within the diamino-diimido compartment. Moreover, both functionalization of the primary amines with bulky substituents and apical coordination of Cu(2+) make access to the 3+ oxidation state more difficult and disrupt the reversibility of the electrochemical process.

The effect of extended H 2 sorption cycles on the structure and on the hydrogen storage performances of MgH 2 powders with 5 wt% of Fe particle catalyst is reported. MgH 2 powders with and without Fe have been ball milled under Argon, the doped MgH 2 nanocomposite has been cycled under hydrogen pressure up to a maximum of 47 desorption and absorption cycles at 300 °C. After acceleration during the first 10 cycles, the kinetics behavior of doped MgH 2 is constant after extended cycling, in terms of maximum storage capacity and rate of sorption. The major effect of cycling on particle morphology is the progressive extraction of Mg from the MgO shell surrounding the powder particles. The Mg extraction from the MgO shell leaves the catalyst particles inside the hydride particles. Many empty MgO shells are observed in the pure ball milled MgH 2 upon cycling at higher temperature, suggesting that this enhancement of the extraction efficiency is related to the higher operating temperature which favors Mg diffusivity with respect to the H ion one.