A Series of Octanuclear-Nickel(II) Complexes Supported by Thiacalix[4]arenes

A series of discrete complexes, [Ni-8(BTC4A)(2)(mu(6)-CO3)(2)(mu-CH3COO)(4)(dma)(4)]center dot H2O, [Ni-8(BTC4A)(2)(mu(6)-CO3)(2)(mu-cl)(2)(mu-HCOO)(2)(dma)(4)]center dot 2DMF center dot 2CH(3)CN (2), [Ni-8(PTC4A)(2)(mu(6)-CO3)(2)(mu-CH3COO)(4)(dma)(4)]center dot DMF (3), and [Ni-8(PTC4A)(2)(mu(6)-CO3)(2)(mu-OH)(mu-HCOO)(4)(dma)(4)] (4) (p-tert-butylthiacalix[4]arene = H(4)BTC4A, p-phenylthiacalix[4]arene = H(4)PTC4A, dma = dimethylamine, and DMF = N,N'-dimethylformamide), have been prepared under solvothermal conditions and structurally characterized by singlecrystal 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 thiacalix[4]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 thiacalix[4]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.