Two Mn6 single-molecule magnets with sulfur-contained capping ligand

The reactions of Mn(ClO4)2·6H2O, 1-(2-hydroxyphenyl)ethanone oxime (abbr. as MeSao), NEt3 and thiophene-2-carboxylic acid/thiophene-3-carboxylic acid (2-TCA/3-TCA) lead to [Mn6O2(MeSao)6(2-TCA)2(EtOH)4(H2O)2](EtOH)2 (1) and [Mn6O2(MeSao)6(3-TCA)2(EtOH)4(H2O)2](EtOH)2 (2), respectively. Their structures can be described as a core of the [MnIII6O2(Mesao)6(O2C-thiophene)2(EtOH)4] consisting two off-set, stacked [MnIII3(μ3-O2−)]7+ triangular subunits linked by two central oximato O-atoms and two O-atoms from phenoxide group. Magnetic investigation revealed that 1 and 2 all have a spin ground state S = 4, and both complexes show single-molecule magnet behaviors with similar energy barriers Ueff ∼45 K.