Linked Nickel Metallacrowns from a Phosphonate/2-Pyridyloximate Blend of Ligands: Structure and Magnetic Properties

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• 作者：Albert Escuer ; Júlia Mayans ; Mercè Font-Bardia
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：March 21, 2016
• 年：2016
• 卷：55
• 期：6
• 页码：3161-3168
• 全文大小：427K
• ISSN：1520-510X

文摘

In the present work, four new Ni^II clusters with nuclearities ranging between Ni₄ and Na₂Ni₈ were synthesized, employing the versatile ligand phenylphosphonate and 6-methylpyridylaldoximate as the coligand. Crystallographic data show that the tetranuclear complex [Ni₄(6-MepaoH)₄(PhPO₃)₂(OH)₂(MeOH)₄](OH)₂ (1) consists of two dimers linked by phosphonate bridges, whereas [Cs₂Ni₆(6-Mepao)₆(PhPO₃)₃(OH)₂(H₂O)₈] (2), Cs[Ni₈(6-MepaoH)₆(6-Mepao)₆(PhPO₃)₃](ClO₄)₅ (3), and [Ni₈Na₂(BzO)₆(6-Mepao)₆(PhPO₃)₃] (4) are built from phosphonato-linked {Ni₃(6-Mepao)₃} metallacycles. The [9-MC_{Ni^II(6-Mepao)}-3] fragments in 2–4 show the unusual coordination of additional Cs⁺, Na⁺, and/or Ni^II cations. Direct-current magnetic measurements were carried in the 300–2 K range. Analysis of the experimental data revealed a complex response with strong antiferromagnetic interactions mediated by the oximato bridges and weak interactions mediated by the phosphonate ones.