A series of octanuclear-nickel(II) complexes supported by thiacalix[4]arenes

A series of discrete complexes, Ni(8)(BTC4A)(2)(μ(6)-CO(3))(2)(μ-CH(3)COO)(4)(dma)(4)]·H(2)O (1), Ni(8)(BTC4A)(2)(μ(6)-CO(3))(2)(μ-Cl)(2)(μ-HCOO)(2)(dma)(4)]·2DMF·2CH(3)CN (2), Ni(8)(PTC4A)(2) (μ(6)-CO(3))(2)(μ-CH(3)COO)(4)(dma)(4)]·DMF (3), and Ni(8)(PTC4A)(2)(μ(6)-CO(3))(2)(μ-OH)(μ-HCOO)(3) (dma)(4)] (4) (p-tert-butylthiacalix4]arene = H(4)BTC4A, p-phenylthiacalix4]arene = H(4)PTC4A, dma = dimethylamine, and DMF = N,N'-dimethylformamide), have been prepared under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analyses, powder XRD, and IR spectroscopy. These four complexes are stacked by dumbbell-like building blocks with one chairlike octanuclear-nickel(II) core, which is capped by two thiacalix4]arene molecules and connected by two in situ generated carbonato anions and different auxiliary anions. This work implied that not only the solvent molecules but also the upper-rim groups of thiacalix4]arenes have significant effects on the self-assembly of the dumbbell-like building blocks. The magnetic properties of complexes 1-4 were examined, indicating strong antiferromagnetic interactions between the nickel(II) ions in the temperature range of 50-300 K.