Mn7 and Mn12 Clusters From Use of 2-(Pyridine-2-yl)propan-2-ol: A New Half-Integer Single-Molecule Magnet

Abstract

The syntheses, crystal structures, and magnetochemical characterization are reported for two new Mn clusters, [Mn(7)O(3)(OH)(3)(O(2)CBu(t))(7)(dmhmp)(4)] (1) and [Mn(12)O(7)(OH)(OMe)(2)(O(2)CPh)(12)(dmhmp)(4)(H(2)O)] (2). They were obtained from the use of 2-(pyridine-2-yl)propan-2-ol (dmhmpH), a more bulky version of the 2-(hydroxymethyl)pyridine (hmpH) reagent commonly employed previously in Mn chemistry. The reaction of dmhmpH with MnCl(2).4H(2)O and NaO(2)CBu(t) in MeCN/MeOH led to the heptanuclear complex 1, whereas the analogous reaction with Mn(O(2)CPh)(2) gave dodecanuclear complex 2. Complexes 1 and 2 are both mixed-valent and are of unprecedented structural types. Complex 1 (Mn(II), 6Mn(III)) can be described as the fusion of butterfly-like [Mn(4)(mu(3)-O)(2)] and tetrahedral [Mn(4)(mu(4)-O)] units by the sharing of a common Mn atom. Complex 2 (3Mn(II), 9Mn(III)) possesses a central [Mn(4)O(6)] face-sharing incomplete dicubane, on either side of which is a tetrahedral [Mn(4)(mu(4)-O)] unit attached to the oxide ions of the former. Solid-state dc and ac magnetic susceptibility measurements on 1 and 2 establish that they possess unusual S = 7/2 and 13/2 ground states, respectively. The ac susceptibility studies on 2 revealed nonzero frequency-dependent out-of-phase (chi(M)'') signals at temperatures below 3 K, indicating a single-molecule magnet (SMM). Magnetization versus applied dc field sweeps on single crystals of 2.3CH(2)Cl(2) down to 0.04 K exhibited hysteresis, thus confirming complex 2 to be a new half-integer SMM.