Issue 7, 2010

Chiral transition metal clusters from two enantiomeric schiff base ligands. Synthesis, structures, CD spectra and magnetic properties

Abstract

Two enantiomeric Schiff base ligands R-/S-H2Lin situ generated from the condensation of o-vanillin with R- or S-2-phenylglycinol were applied to assemble chiral multinuclear transition metal magnetic clusters for the first time. Four new enantiomerically pure chiral clusters, [NaMn43-O)(N3)1.75Br0.25(R-L)3(MeOH)2(H2O)2][NaMn43-O)(N3)2(R-L)3(MeOH)2(H2O)2]Br4 (1R), [NaMn43-O)(N3)1.75Br0.25(S-L)3(MeOH)2(H2O)2][NaMn43-O)(N3)2(S-L)3(MeOH)2(H2O)2]Br4 (1S), [Cu6(R-L)2(R-HL)2(N3)5(MeOH)]NO3·2MeOH·H2O (2R) and [Cu6(S-L)2(S-HL)2(N3)5(MeOH)]NO3·2MeOH·H2O (2S), have been synthesized and characterized by single crystal X-ray crystallography and CD spectroscopy. Three Mn(III) in the MnIIMnIII3 clusters of 1R and 1S are joined together through the μ3-O bridge to form an oxo-centered Mn3O unit. Three L2− link four manganese atoms via the μ2-O,N,O-bridging manner into a MnIIMnIII3 cluster in a distorted tetrahedral geometry. Enantiomeric 2S and 2R are hexanuclear copper(II) clusters composed of a cubane-like Cu4L4 part with a dinuclear Cu2(N3)2 unit capped on one of the faces of the Cu4L4 cubane via the μ1,1-azide and phenolate bridges from the chiral ligands. Magnetic analysis reveals intracluster antiferromagnetic interaction between adjacent manganese ions in chiral oxo-centered MnIIMnIII3 magnetic clusters for 1R and 1S, and dominating antiferromagnetic over weak ferromagnetic interactions in Cu6 clusters in 2R and 2S.

Graphical abstract: Chiral transition metal clusters from two enantiomeric schiff base ligands. Synthesis, structures, CD spectra and magnetic properties

Supplementary files

Article information

Article type
Paper
Submitted
18 Aug 2009
Accepted
19 Nov 2009
First published
24 Dec 2009

Dalton Trans., 2010,39, 1771-1780

Chiral transition metal clusters from two enantiomeric schiff base ligands. Synthesis, structures, CD spectra and magnetic properties

L. Fan, F. Guo, L. Yun, Z. Lin, R. Herchel, J. Leng, Y. Ou and M. Tong, Dalton Trans., 2010, 39, 1771 DOI: 10.1039/B917091J

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