Single-molecule magnets: a new family of Mn(12) clusters of formula [Mn(12)O(8)X(4)(O(2)CPh)(8)L(6)

The reaction of (NBu(n)(4))[Mn(8)O(6)Cl(6)(O(2)CPh)(7)(H(2)O)(2)] (1) with 2-(hydroxymethyl)pyridine (hmpH) or 2-(hydroxyethyl)pyridine (hepH) gives the Mn(II)(2)Mn(III)(10) title compounds [Mn(12)O(8)Cl(4)(O(2)CPh)(8)(hmp)(6)] (2) and [Mn(12)O(8)Cl(4)(O(2)CPh)(8)(hep)(6)] (3), respectively, with X = Cl. Subsequent reaction of 3 with HBr affords the Br(-) analogue [Mn(12)O(8)Br(4)(O(2)CPh)(8)(hep)(6)] (4). Complexes 2.2Et(2)O.4CH(2)Cl(2), 3.7CH(2)Cl(2), and 4.2Et(2)O.1.4CH(2)Cl(2) crystallize in the triclinic space group P1, monoclinic space group C2/c, and tetragonal space group I4(1)/a, respectively. Complexes 2 and 3 represent a new structural type, possessing isomeric [Mn(III)(10)Mn(II)(2)O(16)Cl(2)] cores but with differing peripheral ligation. Complex 4 is essentially isostructural with 3. A magnetochemical investigation of complex 2 reveals an S = 6 or 7 ground state and frequency-dependent out-of-phase signals in ac susceptibility studies that establish it as a new class of single-molecule magnet. These signals occur at temperatures higher than those observed for all previously reported single-molecule magnets that are not derived from [Mn(12)O(12)(O(2)CR)(16)(H(2)O)(x)]. A detailed investigation of forms of complex 2 with different solvation levels reveals that the magnetic properties of 2 are extremely sensitive to the latter, emphasizing the importance to the single-molecule magnet properties of interstitial solvent molecules in the samples. In contrast, complexes 3 and 4 are low-spin molecules with an S = 0 ground state.