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dc.contributor.authorSetifi, Fatima
dc.contributor.authorSetifi, Zouaoui
dc.contributor.authorKonieczny, Piotr
dc.contributor.authorGlidewell, Christopher
dc.contributor.authorBenmansour, Samia
dc.contributor.authorGómez-García, Carlos J.
dc.contributor.authorGrandjean, Fernande
dc.contributor.authorLong, Gary J.
dc.contributor.authorPelka, Robert
dc.contributor.authorReedijk, Jan
dc.identifier.citationSetifi , F , Setifi , Z , Konieczny , P , Glidewell , C , Benmansour , S , Gómez-García , C J , Grandjean , F , Long , G J , Pelka , R & Reedijk , J 2018 , ' Synthesis, structure and magnetic properties of an unusual oligonuclear iron(III)-cobalt(III) compound with oxido-, sulfato- and cyanido-bridging ligands ' , Polyhedron , vol. In press .
dc.identifier.otherPURE: 256213959
dc.identifier.otherPURE UUID: 49adab5e-9655-463c-801e-88211f71eabe
dc.identifier.otherRIS: urn:07523E492DD89B2136521FEF023B3EA3
dc.identifier.otherScopus: 85055904375
dc.identifier.otherWOS: 000451791000068
dc.descriptionThe authors are in debt to the Algerian DG-RSDT (Direction Générale de la Recherche Scientifique et du Développement Technologique) and Université Ferhat Abbas Sétif 1 for financial support. SZ thanks Dr Ewa Juszyńska-Gałązka, from the Institute of Nuclear Physics Polish Academy of Sciences, for performing FT-IR measurements using EXCALIBUR FTS-3000 spectrometer. The magnetic part was supported by the Generalitat Valenciana (PrometeoII/2014/076 project) and the Spanish MINECO (project CTQ2017-87201-P AEI/FEDER, UE).en
dc.description.abstractThe synthesis, characterization, structure and magnetic properties of a hexametallic mixed-metal iron(III)-cobalt(III) compound are described. The compound has been characterized by standard spectroscopic and analytical methods to determine its composition. Single-crystal X-ray diffraction has shown that the asymmetric unit consists of discrete dinuclear dicationic units of {(µ-oxido-µ-[sulfato–O1,O2])bis[tris(2-pyridyl-methyl)amineiron(III)]}2+, herein designated as Fe12, and two half-dinuclear dianionic units of {(µ-oxido)bis[iron(III)]}2– units, herein designated as Fe33a and Fe44b, generating the overall composition Co2Fe4O2(CN)12(tpa)4, 1 , where tpa is tris(2-pyridylmethyl)amine. X-ray structural results and thermogravimetric and differential scanning calorimetry measurements also indicate that the compound, depending upon its history may contain up to nine interstitial waters of hydration, herein designated as 1 (H2O)9. In the dinuclear dicationic unit, the bridging Fe–O–Fe bond in Fe12 is bent and there is also an Fe-O-S-O-Fe sulfato-based bridge with an angle of 132.8°. In contrast, in the two dinuclear dianionic units, Fe33a and Fe44b, the Fe–O–Fe bond angle is crystallographically constrained to be linear. The Co–CN–Fe bonds are almost co-linear, with Co–C–N angles of 176° and C–NFe angles of 169°–. In each species the tpa ligand is tripodal tetradentate with the tertiary amine trans to the sulfato ligand or to the cyanide ligand in the dianions or the bridged oxido ligand in the dications. Bond lengths and angles are all in the typical range for Fe(III) and Co(III) compounds. The magnetic behavior of 1 (H2O)9, obtained upon cooling from 300 to 2 K, reveals a strong antiferromagnetic interaction between the Fe(III) ions in each dinuclear unit. Attempts to discriminate between the two Fe(III) dinuclear units in 1 (H2O)9 have in all cases led to two very different Heisenberg isotropic exchange coupling constants, namely J= –220(2) and –716(32) cm–1 for 1 (H2O)9; i.e.. one of the dinuclear units, probably the Fe12 unit, is so strongly antiferromagnetically coupled that it is close to diamagnetic between 2 and ca. 250 K and has a Heisenberg S = 0 ground state.
dc.rightsCopyright © 2018 Published by Elsevier Ltd. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at:
dc.subjectQD Chemistryen
dc.titleSynthesis, structure and magnetic properties of an unusual oligonuclear iron(III)-cobalt(III) compound with oxido-, sulfato- and cyanido-bridging ligandsen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.description.statusPeer revieweden

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