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Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Towards ionic liquids with tailored magnetic properties: bmim+ salts of ferro- and antiferromagnetic Cu triangles
Athanassios K Boudalis1, Guillaume Rogez2, Benoît Heinrich2
1Department of Chemistry and Biochemistry and the Biomolecular Sciences Institute, Florida International University, Miami, FL 33199, USA and Institut de Chimie de Strasbourg (UMR 7177, CNRS-Unistra), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, F-67081 Strasbourg, France. bountalis@unistra.fr.
Abstract:
Complexes (bmim)2[Cu3(μ3-Cl)2(μ-pz)3Cl3] (1), (bmim)[Cu3(μ3-OH)(μ-pz)3Cl3] (2) and (bmim)2[Cu3(μ3-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.
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