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Compartmentalization of Alkaline-Earth Metals in Salen-Type Cu- and Ni-Complexes in Solution and in the Solid State

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journal contribution
posted on 13.06.2019 by Alba Finelli, Nelly Hérault, Aurélien Crochet, Katharina M. Fromm
The precise arrangement of metal ions in type and number by a ligand represents an important challenge in biology as well as in materials science. The preorganization of different metal ions such as alkaline-earth and transition-metal ions is of particular interest for the design of catalysts or precursors of oxides. This study is based on a Ω-shaped salen-derived ligand comprising N2O2 and O2O2 coordination sites. The selective binding of Cu­(II) and Ni­(II) and alkaline-earth-metal ions is influenced by many factors such as the size of the cation, the solvent, or the counterion. UV–vis and 1H NMR titrations and single-crystal X-ray structures reveal that the obtained complexes tend to adopt different structures in solution compared to the solid state. Mainly discrete motifs with a stoichiometry 1:1 (LM1 to alkaline-earth-metal ions) have been shown to form in the solid state, whereas in solution, the 2:1 complexes are predominant.