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Issue 45, 2016
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Two unprecedented decanuclear heterometallic [MnII2MnIII6LnIII2] (Ln = Dy, Tb) complexes displaying relaxation of magnetization

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Abstract

We report the syntheses, crystal structures, and magnetic properties of two 3d–4f heterometallic compounds; namely, [Mn8Ln2O2(OH)2{(py)2CO2}4(teaH)4(CH3COO)6]·6CH3CN·2H2O (LnIII = Dy (1), Tb (2); (py)2CO2H2 = the gem-diol form of di-2-pyridyl ketone, teaH3 = triethanolamine). Both compounds were prepared by the reaction of Mn(OAc)2·4H2O, Ln(NO3)3·5H2O (Ln = Dy and Tb) with the ligands di-2-pyridyl ketone and triethanolamine in MeCN, and they crystallize in the monoclinic space group C2/c. [Mn8Ln2] complexes have not been reported before, and the metallic cores of both complexes were unprecedented. In these cores, two Dy or Tb and two Mn ions comprised a well-known butterfly topology, with three of the remaining six Mn atoms each being situated on either side of the butterfly, linked through two μ3-O2− ions. Six MnIII and two MnII were in six-coordinated distorted octahedrons and two LnIII ions were in nine-coordinated distorted muffins. Interestingly, the coordination sites of LnIII ions are occupied by six O and two N atoms from two teaH2− ligands and one μ3-O2− atom, without the presence of coordinated solvent molecules such as H2O and small anions such as NO3 ions, which is rare in 3d–4f complexes. Remarkably, alternating current (ac) magnetic susceptibility measurements revealed that both complexes displayed dynamic anisotropic magnetic behaviour. The effective energy barrier (Ueff) of complex 2 was estimated to be 18.97 K through high frequency (111–9111 Hz) ac susceptibility measurements. The low symmetry of the coordination configuration of Ln3+ in 1 and 2 may be responsible for the small energy barriers of these two compounds.

Graphical abstract: Two unprecedented decanuclear heterometallic [MnII2MnIII6LnIII2] (Ln = Dy, Tb) complexes displaying relaxation of magnetization

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Publication details

The article was received on 25 Jul 2016, accepted on 11 Oct 2016 and first published on 11 Oct 2016


Article type: Paper
DOI: 10.1039/C6DT02945K
Citation: Dalton Trans., 2016,45, 18221-18228
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    Two unprecedented decanuclear heterometallic [MnII2MnIII6LnIII2] (Ln = Dy, Tb) complexes displaying relaxation of magnetization

    H. Wang, F. Yang, Q. Long, Z. Huang, W. Chen, Z. Pan and Y. Song, Dalton Trans., 2016, 45, 18221
    DOI: 10.1039/C6DT02945K

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