Single-molecule magnets:: Structure and properties of [Mn18O14(O2CMe)18(hep)4(hepH)2(H2O)2](ClO4)2 with spin S=13

The reaction of 2-(hydroxyethyl)pyridine (hepH) with a 2:1 molar mixture of [Mn3O(O2CMe)(6)(PY)(3)]ClO4 and [Mn3O(O2CMe)(6)(PY)(3)] in MeCN afforded the new mixed-valent (16Mn(III), 2Mn(II)), octadecanuclear complex [Mn18O14(O2CMe)(18)(hep)(4)(hepH)(2)(H2O)(2)](Clo(4))(2) (1) in 20% yield. Complex 1 crystallizes in the triclinic space group P1. Direct current magnetic susceptibility studies in a 1.0 T field in the 5.0-300 K range, and variable-temperature variable-field dc magnetization studies in the 2.0-4.0 K and 2.0-5.0 T ranges were obtained on polycrystalline samples. Fitting of magnetization data established that complex 1 possesses a ground-state spin of S = 13 and D = -0.18 K. This was confirmed by the value of the in-phase ac magnetic susceptibility signal. Below 3 K, the complex exhibits a frequency-dependent drop in the in-phase signal, and a concomitant increase in the out-of-phase signal, consistent with slow magnetization relaxation on the ac time scale. This suggests the complex is a single-molecule magnet (SMM), and this was confirmed by hysteresis loops below 1 K in magnetization versus dc field sweeps on a single crystal. Alternating current and direct current magnetization data were combined to yield an Arrhenius plot from which was obtained the effective barrier (U-eff) for magnetization reversal of 21.3 K. Below 0.2 K, the relaxation becomes temperature-independent, consistent with relaxation only by quantum tunneling of the magnetization (QTM) through the anisotropy barrier via the lowest-energy M-S = +/-13 levels of the S = 13 spin manifold. Complex 1 is thus the SMM with the largest ground-state spin to display QTM.