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

A series of discrete complexes, [Ni₈(BTC4A)₂(μ₆-CO₃)₂(μ-CH₃COO)₄(dma)₄]·H₂O (<b>1</b>), [Ni₈(BTC4A)₂(μ₆-CO₃)₂(μ-Cl)₂(μ-HCOO)₂(dma)₄]·2DMF·2CH₃CN (<b>2</b>), [Ni₈(PTC4A)₂ (μ₆-CO₃)₂(μ-CH₃COO)₄(dma)₄]·DMF (<b>3</b>), and [Ni₈(PTC4A)₂(μ₆-CO₃)₂(μ-OH)­(μ-HCOO)₃ (dma)₄] (<b>4</b>) (<i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene = H₄BTC4A, <i>p</i>-phenylthiacalix­[4]­arene = H₄PTC4A, dma = dimethylamine, and DMF = <i>N</i>,<i>N</i>′-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 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 <b>1</b>–<b>4</b> were examined, indicating strong antiferromagnetic interactions between the nickel­(II) ions in the temperature range of 50–300 K