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<p>The first molecular complexes of paramagnetic 3<i>d</i> (Mn, Fe) and 4<i>f</i> (Dy) metals with the pentadentate N<sub>3</sub>S<sub>2</sub> ligand 2,6-diacetylpyridine bis(4-<i>N</i>-(4-ethylphenyl)thiosemicarbazone) (H<sub>2</sub>L) were synthesized: [Mn<sup>II</sup>(H<sub>2</sub>L)Cl(CH<sub>3</sub>OH)]Cl·2.5CH<sub>3</sub>OH (<b>I</b>), [Fe<sup>III</sup>(HL)Cl(CH<sub>3</sub>OH)]Cl (<b>II</b>), and [Dy<sup>III</sup>(L)(HL')]·4CH<sub>3</sub>OH (<b>III</b>). According to X-ray data (CCDC nos. 2 472 028 (<b>I</b>), 2 472 029 (<b>II</b>), 2 472 030 (<b>III</b>)), all complexes are mononuclear. Complexes of the 3<i>d</i> metals <b>I</b> and <b>II</b> have pentagonal-bipyramidal coordination of the magnetic center: the equatorial plane is formed by the pentadentate N<sub>3</sub>S<sub>2</sub> ligand, and the apical positions are occupied by two Cl and O atoms of monodentate axial ligands. The chelating ligand is the neutral H<sub>2</sub>L in the Mn(II) complex and the monodeprotonated HL<sup>–</sup> in the Fe(III) complex. In the 4<i>f</i>-metal complex, two ligands are coordinated to one Dy(III) center: the doubly deprotonated L<sup>2–</sup> and the transformed ligand (HL')<sup>–</sup>, in which one S atom is substituted by a MeO group. As a result, the Dy ion has a nine-coordinate environment DyN<sub>7</sub>S<sub>2</sub>. The magnetic properties of the Fe(III) complex were studied.</p>

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Molecular Mn(II), Fe(III), and Dy(III) Complexes with the Pentadentate N3S2 Ligand

  • 期刊论文

  • 发表日期：

    2025年10月1日

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  • V. D. Sasnovskaya,
  • L. V. Zorina,
  • S. V. Simonov,
  • M. V. Zhidkov,
  • A. I. Dmitriev,
  • D. V. Korchagin,
  • E. B. Yagubskii

摘要

The first molecular complexes of paramagnetic 3d (Mn, Fe) and 4f (Dy) metals with the pentadentate N3S2 ligand 2,6-diacetylpyridine bis(4-N-(4-ethylphenyl)thiosemicarbazone) (H2L) were synthesized: [MnII(H2L)Cl(CH3OH)]Cl·2.5CH3OH (I), [FeIII(HL)Cl(CH3OH)]Cl (II), and [DyIII(L)(HL')]·4CH3OH (III). According to X-ray data (CCDC nos. 2 472 028 (I), 2 472 029 (II), 2 472 030 (III)), all complexes are mononuclear. Complexes of the 3d metals I and II have pentagonal-bipyramidal coordination of the magnetic center: the equatorial plane is formed by the pentadentate N3S2 ligand, and the apical positions are occupied by two Cl and O atoms of monodentate axial ligands. The chelating ligand is the neutral H2L in the Mn(II) complex and the monodeprotonated HL– in the Fe(III) complex. In the 4f-metal complex, two ligands are coordinated to one Dy(III) center: the doubly deprotonated L2– and the transformed ligand (HL')–, in which one S atom is substituted by a MeO group. As a result, the Dy ion has a nine-coordinate environment DyN7S2. The magnetic properties of the Fe(III) complex were studied.