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Updated: May 31, 2026

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Ferromagnetic and antiferromagnetic copper(II) complexes: counterplay between zero-field effects of the quartet
Z Boulsourani1, V Tangoulis, C P Raptopoulou
1Department of General and Inorganic Chemistry, School of Chemistry, Aristotle University of Thessaloniki, Thessaloniki, 54124, Greece.
Abstract:
The linear trinuclear Cu(II) complexes [Cu(3)(L(1))(4)(H(2)tea)(2)] (1), [Cu(3)(L(2))(4)(H(2)tea)(2)]·2CH(3)CN (2), [Cu(3)(L(2))(4)(H(2)tea)(2)] (3), [Cu(3)(L(1))(2)(H(2)tea)(2)(NO(3))(2)] (4) and the dinuclear complex [Cu(2)(L(1))(2)(H(2)tea)(2)] (5), where L(1) = 2-thiophene carboxylate, L(2) = 2-(thiophen-2-yl)-acetate and H(2)tea = the single deprotonated form of triethanolamine have been prepared and characterised while the crystal structures of 1-4 have been determined. The variable-temperature magnetic susceptibilities of complexes 1-5 have been measured in the range 2-300 K under various external fields in the range 0.02-1.0 T. X-band EPR spectra of 1-5 compounds were recorded at 4-100 K. Complexes 1, 2 and 3 found to have the same J = 33 cm(-1) and g values 2.16(1), 2.20(1) and 2.16(1) respectively while for 5 J = 15 cm(-1) and g = 2.06(1) revealing a clear ferromagnetic exchange between Cu(II) ions. Complex 4 was found to be antiferromagnetic with J = -28 cm(-1) and g = 2.21(1). The polycrystalline powder X-band EPR spectrum of complexes 1, 2, and 3 at 4 K are dominated by a transition at 1600 G (g = 4.3) which unambiguously identifies the spin of the ground multiplet (S = 3/2) while the antiferromagnetic complex 4 has a derivative centered at g = 2.1 indicative of a ground doublet (S = 1/2). Concerning complex 5 a spectrum of a dominant derivative centered at g = 2.06(1) is observed with a very weak half field transition (ca. 1500 G) indicative of the ferromagnetic nature of the system. Furthermore, for complexes 2 and 3 a strong temperature dependence of this spectroscopic g-factor is revealed and change of the g(eff) from the liquid helium temperature to the room temperature is almost 2 units.
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