New single-molecule magnet based on Mn-12 oxocarboxylate clusters with mixed carboxylate ligands, [Mn12O12(CN-o-C6H4CO2)(12)(CH3CO2)(4)(H2O)(4)]center dot 8CH(2)Cl(2): Synthesis, crystal and electronic structure, magnetic properties

作者：Kushch L A^*; Sasnovskaya V D; Dmitriev A I; Yagubskii E B; Koplak O V; Zorina L V; Boukhvalov D W

来源：Dalton Transactions, 2012, 41(44): 13747-13754.

DOI：10.1039/c2dt31173a

A new high symmetry Mn-12 oxocarboxylate cluster [Mn12O12(CN-o-C6H4CO2)(12)(CH3CO)(4)(H2O)(4)]center dot 8CH(2)Cl(2) (1) with mixed carboxylate ligands is reported. It was synthesized by the standard carboxylate substitution method. 1 crystallizes in the tetragonal space group I4(1)/a. Complex 1 contains a [Mn12O12] core with eight CN-o-C6H4CO2 ligands in the axial positions, four CH3CO2 and four CN-o-C6H4CO2 in equatorial positions. Four H2O molecules are bonded to four Mn atoms in an alternating up, down, up, down arrangement indicating a 1 : 1 : 1 : 1 isomer. The Mn12 molecules in 1 are self-assembled by complementary hydrogen C-H center dot center dot center dot N bonds formed with participation of the axial o-cyanobenzoate ligands of the adjacent Mn12 clusters. The lattice solvent molecules (CH2Cl2) are weakly interacted with Mn12 units that results in solvent loss immediately after removal of the crystals from the mother liquor. The electronic structure and the intramolecular exchange parameters have been calculated. Mn 3d bands of 1 are rather broad, and the center of gravity of the bands shifts down from the Fermi level. The overlap between Mn 3d bands and 2p ones of the oxygen atoms from the carboxylate bridges is higher than in the parent Mn-12-acetate cluster. These changes in the electronic structure provide a significant difference in the exchange interactions in comparison to Mn12-acetate. The magnetic properties have been studied on a dried (solvent-free) polycrystalline sample of 1. The dc magnetic susceptibility measurements in the 2-300 K temperature range support a high-spin ground state (S = 10). A bifurcation of temperature dependencies of magnetization taken under zero field cooled and field cooled conditions observed below 4.5 K is due to slow magnetization relaxation. Magnetization versus applied dc field exhibited a stepwise hysteresis loop at 2 K. The ac magnetic susceptibility data revealed the frequency dependent out-of-phase (chi(M)'') signals characteristic of single-molecule magnets.

• 出版日期2012