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Updated: Jul 6, 2026
Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Heterometallic integer-spin analogues of S = 9/2 Mn4 cubane single-molecule magnets
Patrick L Feng1, Christopher C Beedle, Changhyun Koo
1Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA 92093-0358, USA.
Abstract:
A family of distorted heterometallic cubanes, [Mn (III) 3Ni (II)(hmp) 3O(N 3) 3(O 2CR) 3], where O 2CR (-) is benzoate ( 1), 3-phenylpropionate ( 2), 1-adamantanecarboxylate ( 3), or acetate ( 4) and hmp (-) is the anion of 2-pyridinemethanol, was synthesized and structurally as well as magnetically characterized. These complexes have a distorted-cubane core structure similar to that found in the S = 9/2 Mn 4 cubane family of complexes. Complexes 1, 3, and 4 crystallize in rhombohedral, hexagonal, and cubic space groups, respectively, and have C 3 molecular symmetry, while complex 2 crystallizes in the monoclinic space group Cc with local C 1 symmetry. Magnetic susceptibility and magnetization hysteresis measurements and high-frequency electron paramagnetic resonance (HFEPR) spectroscopy established that complexes 1-4 have S = 5 spin ground states with axial zero-field splitting (ZFS) parameters ( D) ranging from -0.20 to -0.33 cm (-1). Magnetization versus direct-current field sweeps below 1.1 K revealed hysteresis loops with magnetization relaxation, definitely indicating that complexes 1-4 are single-molecule magnets that exhibit quantum tunneling of magnetization (QTM) through an anisotropy barrier. Complex 2 exhibits the smallest coercive field and fastest magnetization tunneling rate, suggesting a significant rhombic ZFS parameter ( E), as expected from the low C 1 symmetry. This was confirmed by HFEPR spectroscopy studies on single crystals that gave the following parameter values for complex 2: gz = 1.98, gx = gy = 1.95, D = -0.17 cm (-1), B 4 (0) = -6.68 x 10 (-5) cm (-1), E = 6.68 x 10 (-3) cm (-1), and B 4 (2) = -1.00 x 10 (-4) cm (-1). Single-crystal HFEPR data for complex 1 gave g z = 2.02, gx = gy = 1.95, D = -0.23 cm (-1), and B 4 (0) = -5.68 x 10 (-5) cm (-1), in keeping with the C 3 site symmetry of this Mn 3Ni complex. The combined results highlight the importance of spin-parity effects and molecular symmetry, which determine the QTM rates.
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