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Magnetic order in a novel 3D oxalate-based coordination polymer {;[Cu(bpy)3][Mn2(C2O4)3]·H2O};n

Jurić, Marijana; Pajić, Damir; Žilić, Dijana; Rakvin, Boris; Molčanov, Krešimir; Popović, Jasminka (2015) Magnetic order in a novel 3D oxalate-based coordination polymer {;[Cu(bpy)3][Mn2(C2O4)3]·H2O};n. Dalton Transactions, 44 . pp. 20626-20635. ISSN 1477-9226

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A heterometallic coordination polymer {;[Cu(bpy)3][Mn2(C2O4)3]·H2O};n (1 ; bpy = 2, 2’-bipyridine) was synthesized using a building-block approach and characterized by IR spectroscopy, single-crystal X-ray diffraction, magnetization measurement, and X-band ESR spectroscopy both on a single crystal and a polycrystalline sample. The molecular structure of 1 is made of a three-dimensional (3D) anionic network [Mn2(C2O4)3]n 2n− and tris-chelated cations [Cu(bpy)3]2+ occupying the vacancies of the framework. In compound 1 magnetic order is confirmed below 12.8 K – magnetization measurements reveal an antiferromagnetic- like network of canted Mn2+ spins with incorporated paramagnetic Cu2+ centres. The ESR spectroscopy distinctly shows the phase transition ; above T ≈ 13 K, single isotropic Lorentzian lines of Mn2+ ions in the high spin state S = 5/2 were observed, while below this temperature, only characteristic Cu2+ signals from cations were detected. Thermal decomposition residues of 1 at different temperatures (800–1000 °C) were analyzed by powder X-ray diffraction ; by heating the sample up to 1000 °C the spinel oxide CuMn2O4 [94.1(2) wt%] was formed. From the refined structural parameters, it could be seen that the obtained spinel is characterized by the inversion parameter δ ∼ 0.8, and therefore the structural formula at room temperature can be written as tet[Cu0.17Mn0.83]oct[Mn1.17Cu0.83]O4.

Item Type: Article
Additional Information: This work has been supported by the Croatian Science Foundation under the projects IP-2014-09-4079, UIP-2014-09-8276 and 1108. The authors are grateful to Dr Zrinka Dragun and Dr Berislav Peric, both from Ruder Boskovic Institute, for performing the metal analysis by atomic absorption spectrometry and useful EPR discussion, respectively.
Uncontrolled Keywords: heterometallic oxalate-based compound; 3D anionic network; CuMn2O4; spinel structure; magetic study
Subjects: NATURAL SCIENCES > Chemistry
NATURAL SCIENCES > Chemistry > Inorganic Chemistry
Divisions: Division of Materials Chemistry
Division of Materials Physics
Division of Physical Chemistry
Project titleProject leaderProject codeProject type
Karakterizacija niskotemperaturne molekulske dinamike sustava s neuređenom rešetkom metodom ESR-DESiReMarina Ilakovac KvederIP-11-2013-1108HRZZ
Multiferični i magnetoelektrični sustavi-FerMaElDamir PajićUIP-09-2014-8276HRZZ
Novi metal-organsi sustavi s oksalatnim i kinoidnim ligandima s podešenim svojstvima pogodnim za primjenu-NMOSBOQLWTPSFPKrešimir MolčanovIP-09-2014-4079HRZZ
Depositing User: Marijana Jurić
Date Deposited: 08 Dec 2016 12:04
DOI: 10.1039/c5dt02933c

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