High-spin Mn wheels

The syntheses, structures, and magnetic properties of the complexes MnIV4MnIII10MnII2O2(OCH3)12(tmp)8(O2CCH3)10].3Et2O (1.3Et2O), MnIV2MnIII18MnII2O6(OCH3)14(O2CCH3)16(tmp)8(HIm)2].2CH3OH (2.2CH3OH), and MnIV2MnIII18MnII2O6(OCH3)14(O2CCH3)16(Br-mp)8(HIm)2].2C6H14.5CH3OH (3.2C6H14.5CH3OH) are reported. The unusual wheel-like complexes were prepared by the treatment of Mn3O(O2CCH3)6(HIm)3](O2CCH3) (HIm = imidazole) with 1,1,1-tris-(hydroxymethyl)propane (H3tmp) (1 and 2) or 2-(bromomethyl)-2-(hydroxymethyl)-1,3-propanediol (Br-mpH3) (3) in the presence of sodium methoxide (NaOCH3, 2, and 3) in CH3OH. Complex 1.3Et2O crystallizes in the triclinic space group P, while complexes 2.2CH3OH and 3.2C6H14.5CH3OH crystallize in the orthorhombic space group Pbca. Direct current magnetic susceptibility data, collected for 1-3 in the respective 1.8-300 K and 0.1-7 T temperature and magnetic-field ranges, afford spin ground-state values of S = 14 +/- 1 for complex 1 and S = 9 +/- 1 for complexes 2 and 3. Alternating current susceptibility measurements performed on all three complexes in the 1.8-10 K temperature range in a 3.5 G oscillating field at frequencies between 50 and 1000 Hz reveal out-of-phase chi"M signals below approximately 3 K. Single-crystal hysteresis loop and relaxation measurements confirm single-molecule magnetism behavior.