Nanospheric [M₂₀(OH)₁₂(maleate)₁₂(Me₂NH)₁₂]⁴⁺ Clusters (M = Co, Ni) with <i>O</i>_<i>h</i> Symmetry

Abstract

Nanospheric hydroxo-bridged clusters of [M(20)(OH)(12)(maleate)(12)(Me(2)NH)(12)](BF(4))(3)(OH)·nH(2)O (M = Co (1), Ni (2)) with O(h) symmetry were afforded under hydrothermal condition with Co(BF(4))(2)·6H(2)O/Ni(BF(4))(2)·6H(2)O and fumaric acid in a DMF/EtOH mixed solvent. They are characterized by elemental analysis, IR, and X-ray diffraction. X-ray single crystal diffraction analyses show that these two complexes are isostructural containing an ideally cubic M(8) core in that each two M atoms are doubly bridged at the edges by one OH(-) and one maleate, while these OH(-) and maleate groups are coordinated further by exterior identical 12 M atoms which construct a perfect M(12) icosahedron to encapsulate the cubic core. To our knowledge, such large clusters with O(h) symmetry are seldom. The variable-temperature magnetic susceptibility studies reveal that these two isostructures exhibit antiferromagnetic interactions.