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Crystal structures and magnetic properties of two series of phenoxo-O bridged dinuclear Ln2 (Ln = Gd, Tb, Dy) complexes

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Abstract

Six dinuclear lanthanide compounds of the formulae [Ln2(3m-L4)2(L2)2(MeOH)2]·6MeOH (Ln = Gd – 1a, Tb – 1b, and Dy – 1c) and [Ln2(3m-L4)2(L2)2(DMF)2] (Ln = Gd – 2a, Tb – 2b, and Dy – 2c; DMF = N,N-dimethylformamide, H23m-L4 = (2-[(E)-(3-metoxysalicylidene)amino]phenol), and HL2 = 1,3-diphenyl-1,3-diketopropane) were prepared and characterized by elemental analysis, FTIR spectroscopy, thermogravimetric measurements, single-crystal X-ray structural analysis, and magnetometry, and Gd2 and Dy2 compounds by ab initio methods as well. The structural analysis revealed the isostructurallity of the compounds within the series of 1a–c and 2a–c. The analysis of the variable temperature magnetic data showed the presence of a weak antiferromagnetic coupling in the Gd2 compounds (J/cm−1 = –0.13 for 1a and J/cm−1 = –0.17 for 2a). The magnetocaloric effect was studied on compound 2a with the maximum value of −ΔSM = 22.9 J kg−1 K−1 at T = 2.0 K and B = 9 T, which is the highest value among the Gd2 double phenoxo-bridged compounds observed up to now. Both the Dy2 compounds (1c and 2c) exhibit slow-relaxation of magnetization in zero external static magnetic field. Magnetic anisotropy, intradimer magnetic coupling and magnetization blocking barriers were also studied by ab initio methods for 1c and 2c.

Graphical abstract: Crystal structures and magnetic properties of two series of phenoxo-O bridged dinuclear Ln2 (Ln = Gd, Tb, Dy) complexes

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Publication details

The article was received on 14 Sep 2017, accepted on 01 Nov 2017 and first published on 01 Nov 2017


Article type: Paper
DOI: 10.1039/C7DT03441E
Citation: Dalton Trans., 2017, Advance Article
  • Open access: Creative Commons BY-NC license
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    Crystal structures and magnetic properties of two series of phenoxo-O bridged dinuclear Ln2 (Ln = Gd, Tb, Dy) complexes

    M. Machata, R. Herchel, I. Nemec and Z. Trávníček, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT03441E

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