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Updated: Jan 22, 2026

Ligand Nano-cluster Arrays in a Supported Lipid Bilayer
Published on: April 23, 2017
Co-existence of ferro- and antiferromagnetic interactions in a hexanuclear mixed-valence CoMnMn cluster sustained by
Oleh Stetsiuk1, Valentyn Synytsia2, Svitlana R Petrusenko2
1MOLTECH-Anjou, UMR 6200, CNRS, UNIV Angers, 2 bd Lavoisier, 49045 ANGERS Cedex, France. narcis.avarvari@univ-angers.fr and Department of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, Kyiv 01601, Ukraine.
Abstract:
The successful utilization of the "direct synthesis" approach yielded the unprecedented hexanuclear complex of formula [Co2MnMn(L1)4Cl2(μ3-O)2(dmf)4]·2dmf (1) (H3L is the Schiff base derived from the condensation of salicylaldehyde and 3-aminopropane-1,2-diol). Single crystal X-ray analysis revealed that 1 crystallizes in the monoclinic system P21/c and it contains a rare mixed-valence {CoMnMn(μ2-O)8(μ3-O)2} core where all metal ions are linked through the phenolato and alkoxo groups of the L3- ligand. Besides the charge balance resulting from the X-ray structure, the oxidation state of the metal ions has been confirmed by XPS spectroscopy. Cryomagnetic studies indicate the coexistence of ferro- (MnIV-MnII, J2 = +1.10(3) cm-1, J3 = +2.19(3) cm-1; MnII-MnII, j = +0.283(3) cm-1) and antiferromagnetic interactions (MnIV-MnIV, J1 = -17.31(4) cm-1), with the six-coordinate CoIII ions being diamagnetic. DFT type calculations were carried out to substantiate these values. The energy diagram for the different spin states using the best-fit parameters shows the occurrence of six low-lying spin states (S = 0-5) which are close in energy but clearly separated from the remaining ones, with the ground spin state being S = 5. Complex 1 is found to be the first example where weak ferromagnetic exchange between MnII ions through the long -O-MnIV-O- pathway takes place.
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