New members of the polynuclear manganese family: MnII2MnIII2 single-molecule magnets and MnII3MnIII8 antiferromagnetic complexes. Synthesis and magnetostructural correlations

The synthesis, crystal structures and magnetic properties are reported for three novel mixed-valence tetranuclear [MnII2MnIII2(HBuDea)2(BuDea)2(EBA)4] (1), [MnII2MnIII2(HBuDea)2(BuDea)2(DMBA)4] (2) and undecanuclear [MnII3MnIII8O4(OH)2(BuDea)6(DMBA)8] (3) clusters, where H2BuDea is N-butyldiethanolamine, HEBA is 2-ethylbutyric acid and HDMBA is 2,2-dimethylbutyric acid. The compounds have been prepared through self-assembly reactions of manganese(II) chloride with H2BuDea and respective carboxylic acid in methanol solution in air, affording 1 with HEBA, and 2 or 3 with HDMBA, depending on the experimental conditions. The single crystal X-ray analysis reveals that 1 and 2 have similar centrosymmetric structures based on the {M4(μ3-O)2(μ-O)4} core, while 3 discloses the unprecedented {M11(μ-O)4(μ3-O)12} one. The Mn4 complexes display single-molecule magnet (SMM) behavior with a S = 9 spin ground state and a high energy barrier Ueff/kB of up to 51 K. The magnetic properties of 2 are successfully modeled with JMnIII–MnIII/hc = 25.7 cm−1 and two JMnIII–MnII/hc constants of 3.1 and −0.93 cm−1 (data correspond to the Ĥ = −JŜ1·Ŝ2 formalism). The Mn11 cluster exhibits a paramagnetic behavior with dominant antiferromagnetic coupling. A possible influence of intermolecular effects and of different peripheries of the magnetic cores designed by using 2-ethylbutyrate (in 1) or 2,2-dimethylbutyrate (in 2) on the magnetic properties of 1 and 2 is discussed. The experimental magnetostructural correlations for the {MnII2MnIII2(μ3-O)2(μ-O)4} cores, supported by broken symmetry DFT calculations, disclose the X–MnIII⋯MnIII angle and MnIII–O distance (where MnIII–X and MnIII–O are axial Jahn–Teller bonds) as the structural factors having the strongest influence on JMnIII–MnIII exchange coupling. It is shown that two JMnIII–MnII constants are necessary for the correct description of magnetic exchange couplings in the {MnII2MnIII2(μ3-O)2(μ-O)4} tetranuclear unit.