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Issue 19, 2011
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Chromium(iii) stars and butterflies: synthesis, structural and magnetic studies of tetrametallic clusters

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Abstract

We report the synthesis, structures and magnetic properties of a series of chromium(III) metal-centered triangle (or “star”) clusters, [Cr4{RC(CH2O)3}2(4,4′-R′2-bipy)3Cl6] [R = Et, R′ = H (2); R = HOCH2, R′ = H (3); R = Et, R′ = tBu (4)], prepared by two-step solvothermal reactions starting from [CrCl3(thf)3]. The product of the first stage of this reaction is the salt [Cr(bipy)2Cl2]2[Cr2Cl8(MeCN)2] (1). In the absence of the diimine, a different family of tetrametallics is isolated: the butterfly complexes [Cr4{EtC(CH2O)3}2{NH(C(R)NH)2}2Cl6] (R = Me (5), Et (6), Ph (7)] where the chelating N-acetimidoylacetamidine NH(C(R)[double bond, length as m-dash]NH)2 ligands are formed in situ via condensation of the nitrile solvents (RCN) under solvothermal conditions. Magnetic measurements show the chromium stars to have an isolated S = 3 ground state, arising from antiferromagnetic coupling between the central and peripheral metal ions, analogous to the well-known Fe(III) stars. Bulk antiferromagnetic ordering is observed at 0.6 K. The butterfly complexes have a singlet ground state, with a low-lying S = 1 first excited state, due to dominant wing-body antiferromagnetic coupling.

Graphical abstract: Chromium(iii) stars and butterflies: synthesis, structural and magnetic studies of tetrametallic clusters

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Article information


Submitted
31 Jan 2011
Accepted
11 Mar 2011
First published
05 Apr 2011

Dalton Trans., 2011,40, 5278-5284
Article type
Paper

Chromium(III) stars and butterflies: synthesis, structural and magnetic studies of tetrametallic clusters

L. J. Batchelor, M. Sander, F. Tuna, M. Helliwell, F. Moro, J. van Slageren, E. Burzurí, O. Montero, M. Evangelisti, F. Luis and E. J. L. McInnes, Dalton Trans., 2011, 40, 5278
DOI: 10.1039/C1DT10172B

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