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Syntheses, crystal-solution structures and magnetic properties of a series of decanuclear heterometallic [LnIII2CoII4CoIII4] (Ln = Eu, Gd, Tb, Dy) clusters

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Abstract

Four unprecedented decanuclear heterometallic [Ln2CoII4CoIII4] clusters based on a diethanolamine ligand (H2dea), namely [Eu2CoII4CoIII4(dea)8(HCOO)4(OH)2(Cl)2(CH3OH)2]Cl2·4CH3OH·2H2O (1), [Gd2CoII4CoIII4(dea)8(HCOO)4(OH)2(Cl)2(CH3OH)2]Cl2·4CH3OH·2H2O (2), [Tb2CoII4CoIII4(dea)8(HCOO)4(OH)2(Cl)2(CH3OH)2]Cl2·2CH3OH·4H2O (3) and [Dy2CoII4CoIII4(dea)8(HCOO)4(OH)2(Cl)2(CH3OH)2]Cl2·2CH3OH·4H2O (4) were synthesized through a facile solution method. Single-crystal X-ray diffraction analyses reveal that complexes 1–4 consist of a [Ln2CoII4CoIII4] core, which is constructed by bridging a quasi-double cuboidal [Ln2CoII2CoIII2] core with two [CoIICoIII] units. Electrospray ionization mass spectrometry (ESI-MS) using methanol solution reveals that complexes 1–4 are stable in the solution, and the clusters undergo three different substitution reactions (Cl replaced by OH, OH replaced by CH3O and HCOO replaced by OH/CH3O) at the same time in the ionization state. Magnetic susceptibilities reveal ferromagnetic couplings within complexes 3 and 4, and the magnetocaloric effect (MCE) for 2 was also evaluated and the maximum entropy change (−ΔSm) value reaches 16.3 J kg−1 K−1 at about 3 K and 5 T.

Graphical abstract: Syntheses, crystal-solution structures and magnetic properties of a series of decanuclear heterometallic [LnIII2CoII4CoIII4] (Ln = Eu, Gd, Tb, Dy) clusters

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Publication details

The article was received on 30 Mar 2018, accepted on 21 Jun 2018 and first published on 27 Jun 2018


Article type: Paper
DOI: 10.1039/C8DT01252K
Citation: Dalton Trans., 2018, Advance Article
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    Syntheses, crystal-solution structures and magnetic properties of a series of decanuclear heterometallic [LnIII2CoII4CoIII4] (Ln = Eu, Gd, Tb, Dy) clusters

    Y. Yu, Y. Hu, Y. Guo, Y. Niu, L. Yang, H. Song, Y. Shen, X. Zheng, S. Hou and G. Feng, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT01252K

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