Heterometallic CoII-CoIII-MII alkoxido-bridged heptanuclear motifs (M=Cu, Zn). Syntheses, crystal structures and magnetic properties

Eliza Martin, Violeta Tudor, Augustin M. Madalan, Catalin Maxim, Floriana Tuna, Francesc Lloret, Miguel Julve, Marius Andruh

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    Two new alkoxido-bridged heterometallic complexes of formula [CoIICoIII 3CuII 3(dea)6(CH3COO)3](ClO4)0.75(CH3COO)1.25 (1) and [CoII 2CoIII 2ZnII 3(tea)2(piv)6(CH3O)2(OH)2(CH3OH)2]·H2O 2 (H2dea=diethanolamine, H3tea=triethanolamine and Hpiv=pivalic acid) have been assembled using aminoalcohol ligands. The cationic core in 1 possesses a threefold crystallographic axis, and it exhibits a set of three copper(II), one cobalt(II) and three cobalt(III) ions arranged as a hexagon of alternating copper(II) and cobalt(III) ions around the central cobalt(II) ion. Each edge of the hexagon is defined by a double alkoxido bridge, the outer one being bis-monodentate with copper(II)-cobalt(III) pair whereas the inner one adopts a tris-monodentate coordination mode linking the Cu(II)-Co(III) pair with the central cobalt(II) ion. The acetate groups act as bidentate ligands towards the copper(II) ions. The intramolecular cobalt(II)-copper(II) separation is 3.157Å. A hexagon of two cobalt(II), two cobalt(II) and two zinc(II) ions distributed along three types of edges with a central zinc(II) ion occurs in 2. A tris-modentate alkoxido bridge is involved in all edges together with another bis-monodentate alkoxido bridge (CoIII-CoII and CoII-ZnII pairs) and a carboxylate-pivalate bridge in the syn-syn conformation. The five coordination at each peripheral zinc(II) ion is completed by a monodentate carboxylate-pivalate ligand whereas a methoxo group allows to achieve the six-coordination at each cobalt(III) ion. The intramolecular cobalt(II)-cobalt(II) separation through the inner zinc(II) ion is 6.309Å. The magnetic properties of 1 and 2 have been investigated in the temperature range 1.9-300K. The exchange interaction between the six-coordinate cobalt(II) and copper(II) ions through the double alkoxido bridges in 1 and that between the six-coordinate cobalt(II) ions across the diamagnetic zinc(II) ion in 2 are found to be ferromagnetic [J =+5.39(5) (1) and +1.05(2)cm-1 (2)], the accidental orthogonality between the interacting magnetic orbitals accounting for this behaviour in the two cases.

    Original languageEnglish
    JournalInorganica Chimica Acta
    Early online date1 Jun 2017
    Publication statusPublished - 2017


    • Cobalt complexes
    • Copper complexes
    • Magnetic properties
    • Mixed-valence clusters
    • Zinc complexes


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