Towards ionic liquids with tailored magnetic properties: bmim + salts of ferro- and antiferromagnetic Cu triangles

Dalton Trans. 2017 Sep 28;46(36):12263-12273. doi: 10.1039/c7dt02472j. Epub 2017 Sep 7.

Abstract

Complexes (bmim)2[Cu33-Cl)2(μ-pz)3Cl3] (1), (bmim)[Cu33-OH)(μ-pz)3Cl3] (2) and (bmim)2[Cu33-OH)(μ-Cl)(μ-pz)3Cl3] (3) were synthesized (bmim+ = 1-butyl-3-methylimidazolium, pz- = pyrazolato anion). Dianionic complexes 1 and 3 were obtained as crystalline solids, whereas the monoanionic complex 2 was obtained as a viscous paste. Magnetic susceptibility and X-band EPR studies revealed intramolecular ferromagnetic interactions for 1 with small magnetoanisotropy in its ground state (D3/2∼ 10-3 cm-1) and intramolecular antiferromagnetic interactions for 2 and 3 (-285 and -98 cm-1 average J, respectively) with important magnetic anisotropy in their ground states stemming from a combination of low magnetic symmetry and antisymmetric exchange interactions. Thermal studies revealed a clear melting point of 140 °C for 1, which is lower than that of its PPN+ and Bu4N+ analogues (1PPN and 1Bu4N, respectively, PPN+ = bis(triphenylphosphine)iminium). Upon cooling, 1 remains molten down to 70 °C. Mixtures of the salts 1, 1PPN and 1Bu4N, exhibited modified melting behaviours, with the mixtures exhibiting lower melting points than those of either of their pure components.