Issue 11, 2013

Systematic studies of the structures and magnetic properties for a family of cubane complexes with the formula: [M2Ln2] (Ln = Dy, Gd; M = Ni, Zn) and [Ni2Y2]

Abstract

Studies of magnetic properties of a family of tetranuclear MII2LnIII2 (M = Ni, Zn; Ln = Dy, Gd and Y) complexes with hmp (anion of 2-hydroxymethylpyridine) and benzoate as ligands are reported. In these complexes, metal ions (M or Ln) occupy the four alternative corners of a distorted cubane with oxygen atoms from alkoxyl groups on the others. Complexes 1, 2 and 3 crystallized in P21/c and complexes 4 and 5 in C2/c space groups. Although in different space groups, complexes 1–5 have very similar structures which permit the magnetic interactions to be systematically compared with respect to metal ion pairs. In complex 3 (Ni2Y2), clear ferromagnetic coupling between NiII ions can be seen, with: g = 2.16, S = 2, D = −0.95 cm−1, J = +3.77 cm−1 (or g = 2.20, S = 2, D = +1.51 cm−1). In complex 5 (Zn2Gd2), a very weak antiferromagnetic coupling between the GdIII ions was observed: g = 2.08, J = −0.05 cm−1. Based on these data, we concluded that the decrease in χMTT upon cooling for complex 2 (Zn2Dy2) might be partly due to antiferromagnetic coupling between DyIII ions. The data from complex 4 (Ni2Gd2) were analyzed based on the preceding results and gave moderate ferromagnetic coupling between NiII and GdIII with J = 0.26 cm−1. A detailed study of magnetic properties of complex 1 (Ni2Dy2) was not possible, because of its strong orbital contributions from DyIII ions. In addition, frequency-dependent out-of-phase signals were clearly observed for both complexes 1 and 2 which can be attributed to magnetoanisotropy contributions from DyIII ions.

Graphical abstract: Systematic studies of the structures and magnetic properties for a family of cubane complexes with the formula: [M2Ln2] (Ln = Dy, Gd; M = Ni, Zn) and [Ni2Y2]

Supplementary files

Article information

Article type
Paper
Submitted
11 Nov 2012
Accepted
19 Dec 2012
First published
18 Jan 2013

Dalton Trans., 2013,42, 3941-3949

Systematic studies of the structures and magnetic properties for a family of cubane complexes with the formula: [M2Ln2] (Ln = Dy, Gd; M = Ni, Zn) and [Ni2Y2]

W. Yu, G. Lee and E. Yang, Dalton Trans., 2013, 42, 3941 DOI: 10.1039/C2DT32688D

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