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Updated: Jun 13, 2026
Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Chiral transition metal clusters from two enantiomeric schiff base ligands. Synthesis, structures, CD spectra and
Lin-Lin Fan1, Fu-Sheng Guo, Lei Yun
1Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, China.
Abstract:
Two enantiomeric Schiff base ligands R-/S-H2L in 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, [NaMn4(3-O)(N3)1.75Br0.25(R-L)3(MeOH)2(H2O)2][NaMn4(mu3-O)(N3)2(R-L)3(MeOH)2(H2O)2]Br4 (1R), [NaMn4(mu3-O)(N3)1.75Br0.25(S-L)3(MeOH)2(H2O)2][NaMn4(mu3-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 3-O bridge to form an oxo-centered Mn3O unit. Three L2- link four manganese atoms via the mu2-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 mu1,1-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.
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