Environmental influence on the single-molecule magnet behavior of [Mn(III)6Cr(III)]3+: molecular symmetry versus...

The structural, spectroscopic, and magnetic properties of a series of [Mn(III)(6)Cr(III)](3+) (= [{(talen(t-Bu(2)))Mn(III)(3)}(2){Cr(III)(CN)(6)}](3+)) compounds have been investigated by single-crystal X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and electronic absorption spectroscopy, elemental analysis, electro spray ionization-mass spectrometry (ESI-MS) and matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS), cyclic voltammetry, AC and DC magnetic measurements, as well as theoretical analysis. The crystal structures obtained with [Cr(III)(CN)(6)](3-) as a counterion exhibit (quasi-)one-dimensional (1D) chains formed by hydrogen-bonded (1) or covalently linked (2) trications and trianions. The rod-shaped anion lactate enforces a rod packing of the [Mn(III)(6)Cr(III)](3+) complexes in the highly symmetric space group R3[overline] (3) with a collinear arrangement of the molecular S(6) axes. Incorporation of the spherical anion BPh(4)(-) leads to less-symmetric crystal structures (4-6) with noncollinear orientations of the [Mn(III)(6)Cr(III)](3+) complexes, as evidenced by the angle between the approximate molecular C(3) axes taking no specific values in the range of 2°-69°. AC magnetic measurements on freshly isolated crystals (1a and 3a-6a), air-dried crystals (3b-6b), and vacuum-dried powder samples (3c-6c) indicate single-molecule magnet (SMM) behavior for all samples with U(eff) values up to 28 K. The DC magnetic data are analyzed by a full-matrix diagonalization of the appropriate spin-Hamiltonian including isotropic exchange, zero-field splitting, and Zeeman interaction, taking into account the relative orientation of the D-tensors. Simulations for 3a-6a and 3c-6c indicate a weak antiferromagnetic exchange between the Mn(III) ions in the trinuclear subunits (J(Mn-Mn) = -0.70 to -0.85 cm(-1), Ĥ(ex) = -2∑(i