Construction of Planar Clusters Using Planar Aromatic Polyoxime Ligands: Synthesis, Structure, and Magnetic Properties
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posted on 2010-11-03, 00:00 authored by Zilu Chen, Maomao Jia, Zhong Zhang, Fupei LiangThe reactions of NiSO<sub>4</sub>·6H<sub>2</sub>O or Mn(CH<sub>3</sub>COO)<sub>2</sub>·4H<sub>2</sub>O with the planar ligands of indane-1,2,3-trione trioxime (H<sub>3</sub>Itto) or indane-1,2,3-trione-1,2-dioxime (H<sub>2</sub>Itdo) gave two planar pentanuclear clusters [Et<sub>3</sub>NH]<sub>2</sub>[Ni<sub>5</sub>(HItto)<sub>4</sub>(MeOH)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub>(SO<sub>4</sub>)<sub>2</sub>]·2H<sub>2</sub>O (<b>1</b>) and [Ni<sub>5</sub>(HItdo)<sub>2</sub>(Itdo)<sub>2</sub>(DMF)<sub>4</sub>(MeOH)(H<sub>2</sub>O)(SO<sub>4</sub>)<sub>2</sub>]·CH<sub>3</sub>OH·6H<sub>2</sub>O (<b>2</b>), one planar trinuclear cluster, [Mn<sup>III</sup><sub>3</sub>(μ<sub>3</sub>-O)(Itdo)<sub>3</sub>(CH<sub>3</sub>COO)(DMF)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]·H<sub>2</sub>O (<b>3</b>), and one planar platelike trinuclear cluster, [Mn<sup>III</sup><sub>3</sub>(μ<sub>3</sub>-O)(Itdo)<sub>3</sub>(CH<sub>3</sub>COO)(DMF)<sub>2</sub>(MeOH)(H<sub>2</sub>O)]·H<sub>2</sub>O (<b>4</b>). Five Ni(II) ions of <b>1</b> and <b>2</b> are consolidated by four indane-1,2,3-trione trioxime ligands and four indane-1,2,3-trione-1,2-dioxime ligands, respectively, to form square topological planar pentanuclear clusters with five Ni(II) ions and all atoms of the four oxime ligands nearly in one plane. However, <b>1</b> and <b>2</b> show some differences in the bridging of the central metal ion with the metal ions on the square corners. Both <b>3</b> and <b>4</b> feature a planar isosceles triangular [Mn<sub>3</sub>(μ<sub>3</sub>-O)]<sup>7+</sup> core. Each edge of the triangular [Mn<sub>3</sub>(μ<sub>3</sub>-O)]<sup>7+</sup> core in <b>3</b> and <b>4</b> is bridged by a μ<sub>2,</sub>η<sup>3</sup>-bridging indane-1,2,3-trione-1,2-dioxime ligand to construct a planar skeleton for <b>3</b> with the central oxygen atom, three Mn(III) ions, and all atoms of the indane-1,2,3-trione-1,2-dioxime ligands nearly in one plane, and a planar platelike skeleton for <b>4</b> with the ligand planes deviating from the triangular metal plane. Magnetic studies of <b>1</b>−<b>4</b> reveal the presence of antiferromagnetic interactions between the metal ions in <b>1</b>−<b>4</b>.
