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Nanospheric [M20(OH)12(maleate)12(Me2NH)12]4+ Clusters (M = Co, Ni) with Oh Symmetry

Author:
Gui, Liu-Cheng, Wang, Xiu-Jian, Ni, Qing-Ling, Wang, Miao, Liang, Fu-Pei, Zou, Hua-Hong
Source:
Journal of the American Chemical Society 2012 v.134 no.2 pp. 852-854
ISSN:
1520-5126
Subject:
X-radiation, X-ray diffraction, cobalt, ethanol, ferrimagnetic materials, fumaric acid, hydroxyl radicals, maleates, nickel, solvents
Abstract:
Nanospheric hydroxo-bridged clusters of [M₂₀(OH)₁₂(maleate)₁₂(Me₂NH)₁₂](BF₄)₃(OH)·nH₂O (M = Co (1), Ni (2)) with Oₕ symmetry were afforded under hydrothermal condition with Co(BF₄)₂·6H₂O/Ni(BF₄)₂·6H₂O 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 M₈ 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 M₁₂ icosahedron to encapsulate the cubic core. To our knowledge, such large clusters with Oₕ symmetry are seldom. The variable-temperature magnetic susceptibility studies reveal that these two isostructures exhibit antiferromagnetic interactions.
Agid:
5385431