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Open Access Research Article Issue
Series of octanuclear clusters of Ni(II)/Co(II) with tunable structures and magnetism supported by thiacalix[4]arenes
Tian Gao, Jiang-Chuan Yu, Ming-Lang Ye, Yan-Ling Liu, Jian-Ping Ma, Long-Sheng Wang, Ya-Min Li
Polyoxometalates 2026, 5(4): 9140141
Published: 16 September 2026
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In this study, five thiacalix[4]arene (TC4A)-based octanuclear homometallic or heterometallic clusters, namely, {[Ni8(TC4A)2(μ6-CO3)2(μ2-CH3CO2)3(μ2-CO3)(DMA)4]}∙(CH3CN)2 (1) (DMA = N,N-dimethylamine), {[Ni5.81Co2.19(TC4A)2(μ6-CO3)2(μ2-HCO2)2(μ2-Cl)2(DMA)4]}∙2DMF∙2CH3CN (2) (DMF = N,N-dimethylformamide), {[Ni4.06Co3.94(TC4A)2(μ6-CO3)2(μ2-HCO2)2(μ2-Cl)2(DMA)4]}∙2DMF∙2CH3CN (3), {[Ni2Co6(TC4A)2(μ6-CO3)2(μ2-HCO2)2(μ2-Cl)2(DMA)4]}∙2DMF∙2CH3CN (4), and {[Co8(TC4A)2(μ6-CO3)2(μ2-HCO2)3(μ2-CO3)2(DMA)4]}∙4DMF (5), are synthesized using a solvothermal method. Single-crystal X-ray diffraction analysis reveals that all synthesized compounds comprise two badminton-like secondary building units (SBUs) [M4(TC4A)] (M = Co, Ni, Co/Ni) linked by two μ6-CO32− anions in a tail-to-tail manner, forming a chair-like octanuclear metal cluster. Their structures were also characterized using Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, X-ray photoelectron spectroscopy, powder X-ray diffraction, etc. Magnetism studies indicate an antiferromagnetic interaction between the metal ions of compounds 1–5, and their magnetic susceptibility χMT increases as the cobalt content increases in the range of 50–300 K. The structures and magnetic properties of the Co(II)/Ni(II) cluster supported by TC4A can be conveniently tuned by varying the Ni(II):Co(II) molar ratio, providing a straightforward approach for fabricating TC4A-based heterometallic clusters.

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