Linked Nickel Metallacrowns from a Phosphonate/2-Pyridyloximate Blend of Ligands: Structure and Magnetic Properties
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Updated: Mar 24, 2026
Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Albert Escuer1, Júlia Mayans1, Mercè Font-Bardia2
1Departament de Química Inorgànica and Institut of Nanoscience and Nanotechnology (IN2UB), Universitat de Barcelona , Avenida Diagonal 645, Barcelona 08028, Spain.
Abstract:
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.
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