A butterfly-like heterometallic [MnIII2DyIII2] tetranuclear pivalate cluster
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DARII, Mariana, HAUSER, J, BOUROSH, Pavlina, KRAMER, Karl W, DECURTINS, Silvio, LIU, Shi-Xia, BACA, Svetlana. A butterfly-like heterometallic [MnIII2DyIII2] tetranuclear pivalate cluster. In: Materials Science and Condensed Matter Physics, Ed. 8-th Edition, 12-16 septembrie 2016, Chişinău. Chişinău: Institutul de Fizică Aplicată, 2016, Editia 8, p. 146. ISBN 978-9975-9787-1-2.
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Materials Science and Condensed Matter Physics
Editia 8, 2016
Conferința "International Conference on Materials Science and Condensed Matter Physics"
8-th Edition, Chişinău, Moldova, 12-16 septembrie 2016

A butterfly-like heterometallic [MnIII2DyIII2] tetranuclear pivalate cluster


Pag. 146-146

Darii Mariana1, Hauser J2, Bourosh Pavlina1, Kramer Karl W2, Decurtins Silvio2, Liu Shi-Xia2, Baca Svetlana1
 
1 Institute of Applied Physics, Academy of Sciences of Moldova,
2 Department of Chemistry and Biochemistry, University of Bern
 
Disponibil în IBN: 29 iulie 2019


Rezumat

During the last decade there has been a tremendous interest in the synthesis, investigation and possible applications of heterometallic 3d-4f clusters. Incorporating lanthanide ions that play a special role in the field of magnetism in 3d molecular clusters provides good starting ingredients for the syntheses of 3d-4f single-molecule magnets.     The reaction of manganese(II) pivalate with Dy(NO3)3·6H2O and triethanolamine ligand in a mixture of EtOH/MeCN results in a new butterfly-like heterometallic [Mn2Dy2O2(piv)8(Hpiv)2(EtOH)2] (1) cluster, where Hpiv = pivalic acid. Single-crystal X-ray diffraction measurements show that compound 1 crystallizes in the monoclinic C2/c space group: a = 27.751(5), b = 13.1825(1), c = 23.931(4) Å, β = 128.14(3)°, V = 6885.96 Å3. The structure consists of a {Mn2Dy2O2}8+ core, where two MnIII and two DyIII centers are connected by two μ3– oxo bridges with Mn…Dy distances of 3.45 Å, and a Mn…Mn distance of 2.854 Å. Each edge of the {Mn2Dy2} rhombus is additionally linked by eight pivalate ligands. The butterfly {Mn2Dy2O2} complex can be also considered as consisting of two edge-sharing heterometallic {Mn2Dy(µ3-O)} triangular subunits. Both pivalate and EtOH complete the coordination sphere for each of the Dy atoms. In 1, MnIII atoms are six–coordinated with a distorted octahedral O6 geometry being coordinated by two μ3-oxo atoms (Mnμ3-O, 1.893(2)-1.900(3) Å), and four oxygen atoms from four pivalate ligands (MnO, 1.958(3)2.185(2) Å). The DyIII atoms are nine–coordinated by 3-O atom (Dy-μ3-O, 2.459(3) Å), six O atoms from four pivalates (Dy-O, 2.472(2)2.493(2) Å) and an O atom (DyO, 2.357(4) Å) from ethanol molecule. The coordinated ethanol and monodentate pivalates establish a system of intra- and intermolecular hydrogen bonds, joining heterometallic clusters into chains as shown in Figure. 1b. The spectroscopic, thermogravimetric and magnetic properties of 1 have also been studied and will be discussed in terms of the known structure. Acknowledgement. The authors thank the Swiss National Science foundation (SCOPES IZ73Z0_152404/1 project) for support.

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<title xml:lang='en,bg,fr'>A butterfly-like heterometallic [MnIII2DyIII2] tetranuclear pivalate cluster</title>
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<description xml:lang='en' descriptionType='Abstract'><p>During the last decade there has been a tremendous interest in the synthesis, investigation and possible applications of heterometallic 3d-4f clusters. Incorporating lanthanide ions that play a special role in the field of magnetism in 3d molecular clusters provides good starting ingredients for the syntheses of 3d-4f single-molecule magnets. &nbsp; &nbsp; The reaction of manganese(II) pivalate with Dy(NO3)3&middot;6H2O and triethanolamine ligand in a mixture of EtOH/MeCN results in a new butterfly-like heterometallic [Mn2Dy2O2(piv)8(Hpiv)2(EtOH)2] (1) cluster, where Hpiv = pivalic acid. Single-crystal X-ray diffraction measurements show that compound 1 crystallizes in the monoclinic C2/c space group: a = 27.751(5), b = 13.1825(1), c = 23.931(4) &Aring;, &beta; = 128.14(3)&deg;, V = 6885.96 &Aring;3. The structure consists of a {Mn2Dy2O2}8+ core, where two MnIII and two DyIII centers are connected by two &mu;3&ndash; oxo bridges with Mn&hellip;Dy distances of 3.45 &Aring;, and a Mn&hellip;Mn distance of 2.854 &Aring;. Each edge of the {Mn2Dy2} rhombus is additionally linked by eight pivalate ligands. The butterfly {Mn2Dy2O2} complex can be also considered as consisting of two edge-sharing heterometallic {Mn2Dy(&micro;3-O)} triangular subunits. Both pivalate and EtOH complete the coordination sphere for each of the Dy atoms. In 1, MnIII atoms are six&ndash;coordinated with a distorted octahedral O6 geometry being coordinated by two &mu;3-oxo atoms (Mn&mu;3-O, 1.893(2)-1.900(3) &Aring;), and four oxygen atoms from four pivalate ligands (MnO, 1.958(3)2.185(2) &Aring;). The DyIII atoms are nine&ndash;coordinated by 3-O atom (Dy-&mu;3-O, 2.459(3) &Aring;), six O atoms from four pivalates (Dy-O, 2.472(2)2.493(2) &Aring;) and an O atom (DyO, 2.357(4) &Aring;) from ethanol molecule. The coordinated ethanol and monodentate pivalates establish a system of intra- and intermolecular hydrogen bonds, joining heterometallic clusters into chains as shown in Figure. 1b. The spectroscopic, thermogravimetric and magnetic properties of 1 have also been studied and will be discussed in terms of the known structure. Acknowledgement. The authors thank the Swiss National Science foundation (SCOPES IZ73Z0_152404/1 project) for support.</p></description>
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