Self-Assembly of Thiacalix[4]arene-Supported Nickel(II)/Cobalt(II) Complexes Sustained by in Situ Generated 5-Methyltetrazolate Ligand

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• 作者：Kecai Xiong ; Feilong Jiang ; Yanli Gai ; Zhangzhen He ; Daqiang Yuan ; Lian Chen ; Kongzhao Su ; Maochun Hong
• 刊名：Crystal Growth & Design
• 出版年：2012
• 出版时间：June 6, 2012
• 年：2012
• 卷：12
• 期：6
• 页码：3335-3341
• 全文大小：381K
• 年卷期：v.12,no.6(June 6, 2012)
• ISSN：1528-7505

文摘

Solvothermal reactions of thiacalix[4]arene, NaN₃, and acetonitrile in the presence of nickel(II)/cobalt(II) salts yielded four discrete complexes sustained by the in situ generated 5-methyltetrazolate ligand, [Ni^II₁₂(PTC4A)₃(渭₆-CO₃)₂(渭-Mtta)₂(渭-Mtta)₄ (渭₄-Mtta)₂(Py)₄]路7DMF路2Py路dma (1), [Co^II₁₂(PTC4A)₃(HCOO)₃(渭₆-CO₃)₂ (渭-Mtta)(渭-Mtta)₂(渭₄-Mtta)₂(Py)₄]路5DMF路dma (2), [Co^II₁₂(BTC4A)₃(HCOO)₂ (渭₆-CO₃)₂(渭-Mtta)₄(渭₄-Mtta)₂(dma)₂(Pz)₂]路2DMF路3dma (3), and [Co^II₁₆(BTC4A)₄(渭₄-Cl)₄ (HCOO)₂(渭-Mtta)₆(渭-Mtta)₈]路10DMF路6CH₃CN路4Hdma (4) (H₄PTC4A = p-phenylthiacalix[4]arene; H₄BTC4A = p-tert-butylthiacalix[4]arene; HMtta = 5-methyl tetrazolate). Crystal structural analyses revealed that complexes 1鈥?b>3 are stacked by pseudotrigonal planar entities, which consist of three metal^II₄-thiacalix[4]arene subunits including two shuttlecock-like and one cylinder-like ones. These subunits are connected in an up-to-down-to-up fashion through six different 5-methyl tetrazolate anions. Both the in situ generated 5-methyl tetrazolate anion and carbonato anion play an important role in constructing these high-nuclearity clusters. When the corresponding chloride salt was used as precursors in the synthesis, complex 4 was obtained, which is stacked by wheel-like entities possessing four shuttlecock-like building blocks linked by eight in situ generated 5-methyl tetrazolate ligands in an up-to-up fashion. The differences in the structures of complexes 3 and 4 indicate that the geometry and size of the corresponding anions together with their coordinating properties are essential in determining the final structures. The magnetic properties of complexes 1鈥?b>4 were examined, indicating strong antiferromagnetic interactions between the nickel(II)/cobalt(II) ions in the temperature range of 50鈥?00 K.