Ultra-low temperature structure determination of a Mn12 single-molecule magnet and the interplay between lattice solvent and structural disorder

We have determined the ultra-low temperature crystal structure of the archetypal single-molecule magnet (SMM) [Mn12O12(O2CMe)16(H2O)4]·4H2O·2MeCO2H (1) at 2 K, by using a combination of single-crystal X-ray and single-crystal neutron diffraction. This is the first structural study of any SMM in the same temperature regime where slow magnetic relaxation occurs. We reveal an additional hydrogen bonding interaction between the {Mn12} cluster and its solvent of crystallisation, which shows how the lattice solvent transmits disorder to the acetate ligands in the {Mn12} complex. Unusual quantum properties observed in 1 have long been attributed to disorder. Hence, we studied the desolvation products of 1, in order to understand precisely the influence of lattice solvent on the structure of the cluster. We present two new axially symmetric structures corresponding to different levels of desolvation of 1, [Mn12O12(O2CMe)16(H2O)4]·4H2O (2) and [Mn12O12(O2CMe)16(H2O)4] (3). In 2, removal of acetic acid of crystallisation largely resolves positional disorder in the affected acetate ligands, whereas removal of lattice water molecules further resolves the acetate ligand disorder in 3. Due to the absence of acetic acid of crystallisation, both 2 and 3 have true, unbroken S4 symmetry, showing for the first time that it is possible to prepare fully axial Mn12–acetate analogues from 1, via single-crystal to single-crystal transformations

Elastic coupling and anelastic relaxation associated with multiple phase transitions in para-chloroanilinium tetrachlorocuprate, [p-ClC6H4NH3]2CuCl4

The perovskite-like salt [p-ClC6H4NH3]2CuCl4 1 exhibits a wealth of magnetic and structural phase transitions which have been probed by variable temperature single crystal X-ray diffraction, SQUID magnetometry, resonant ultrasound spectroscopy (RUS), EPR spectroscopy, DSC measurements and DFT calculations. Single crystal X-ray diffraction studies between room temperature and 3 K reveal a rich tapestry of structural changes; at 298 K the structure conforms to a monoclinic setting but undergoes a first order phase transition upon cooling below ∼275 K to a higher symmetry orthorhombic cell. This is facilitated by a transition to an intermediate phase at ∼277 K. Whilst the intermediate phase has a limited stability window (∼2 K) and has not been structurally determined, the two discrete phase transitions at 275.5 K and 277 K have been clearly detected by differential scanning calorimetry, EPR spectroscopy and RUS studies. On further cooling a dynamic relaxation process is observed in RUS measurements, evidenced by a Debye-like peak in the dissipation at ∼140 K. Residual electron density maps from single crystal X-ray diffraction studies reveal that this may be associated with a freezing out of the NH3⋯Cl hydrogen-bonding between cation and anion frameworks upon cooling. The activation barrier for this order/disorder process was estimated to be at least 27 kJ mol−1 from the RUS data. Variable temperature dc SQUID data reveal that 1 is a 2D ferromagnet with antiferromagnetic interactions between layers below 9 K. Analysis of the temperature dependence of the magnetic susceptibility for T > 40 K reveals that 1 exhibits Curie–Weiss behaviour with θ = +22.8 K indicative of dominant ferromagnetic interactions. Good agreement is observed between the strength of the ferromagnetic interaction extracted from the Weiss constant (J/k = +22.8 K) and that calculated by DFT (J/k = +25 to +28 K) and from EPR studies (J/k = +17 K). The presence of short range ferromagnetic interactions is reflected in a marked temperature dependence of the g-factors determined from EPR spectroscopy below 20 K and possibly a small elastic anomaly in the RUS data. RUS studies indicate a very small elastic anomaly associated with the transition to long range order, implying weak or no magnetoelastic effect. At fields above ∼15 G a spin flip transition is induced and 1 displays metamagnetic behaviour, with a saturation magnetization of 0.96 μB