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From a square core to square opening: structural diversity and magnetic properties of the oxo-bridged [CrIIINbV] complexes

Jurić, Marijana; Androš Dubraja, Lidija; Popović, Jasminka; Molčanov, Krešimir; Torić, Filip; Pajić, Damir; Lončarić, Ivor (2018) From a square core to square opening: structural diversity and magnetic properties of the oxo-bridged [CrIIINbV] complexes. Dalton Transactions, 47 (12). pp. 4183-4190. ISSN 1477-9226

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Three heterometallic oxo-bridged compounds, [Cr2(phen)4(μ-O)4Nb2(C2O4)4]·2H2O (1 ; phen = 1, 10-phenanthroline), [Cr2(terpy)2(H2O)2(μ-O)4Nb2(C2O4)4]·4H2O (2 ; terpy = 2, 2′ ; 6′, 2′′-terpyridine) and [Cr(terpy)(C2O4)(H2O)][Cr2(terpy)2(C2O4)2(μ-O)2Nb(C2O4)2]·3H2O (3), have been synthesized using a building block approach and characterized by IR spectroscopy, single-crystal and powder X-ray diffraction, magnetization measurements, and DFT calculations. The molecular structures of 1 and 2, crystallizing in P42212 and P21/n space groups, respectively, contain a square-shaped {; ; ; ; CrIII2(μ-O)4NbV2}; ; ; ; unit, while that of complex salt 3 (P[1 with combining macron] space group) consists of a mononuclear cation containing CrIII and trinuclear anions in which two CrIII ions are bridged by a –O–NbV–O– fragment. Besides hydrogen-bonding patterns resulting in a 1D- or 3D-supramolecular arrangement in 1–3, an unusual intermolecular contact has been noticed between parallel oxalate moieties occurring due to the electrostatic attraction of electron-rich carbonyl oxygen and severely electron-depleted carbon atoms in the crystal packing of 2. The antiferromagnetic coupling observed in all three compounds, determined from magnetization measurements (J = −13.51(2), −8.41(1) and −7.44(4) cm−1 for 1, 2 and 3, respectively) and confirmed by DFT calculations, originates from two CrIII ions with spin 3/2 interacting through diamagnetic –O–NbV–O– bridge(s).

Item Type: Article
Additional Information: This work has been supported by the Croatian Science Foundation under Project No. IP-2014-09-4079 and UIP-2014-09-8276. I. L. was supported by the Unity Through Knowledge Fund, Contract No. 22/15 and H2020 CSA Twinning Project No. 692194, RBI-T-WINNING.
Uncontrolled Keywords: Oxo-Bridged ; Chromium(III) ; Niobium(V) ; Antiferromagnetic Coupling
Subjects: NATURAL SCIENCES > Physics
Divisions: Division of Materials Chemistry
Project titleProject leaderProject codeProject type
Novi metal-organsi sustavi s oksalatnim i kinoidnim ligandima s podešenim svojstvima pogodnim za primjenu-NMOSBOQLWTPSFPKrešimir MolčanovIP-2014-09-4079HRZZ
Multiferični i magnetoelektrični sustavi-FerMaElDamir PajićUIP-2014-09-8276HRZZ
Ruđer Bošković Institute: Twinning for a step forward of the Theoretical Physics Division-RBI-T-WINNINGFabrizio NESTI692194EK
Depositing User: Marijana Jurić
Date Deposited: 04 May 2020 07:34
DOI: 10.1039/C7DT04724J

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