Magnetic Molecular Rectangles Constructed from Functionalized Nitronyl-Nitroxide Ligands and Lanthanide(III) Ions

Calancea S, Carrella L, Mocanu T, Sadohin V, Raduca M, Gutu I, Da Rocha JC, Vaz MGF, Rentschler E, Andruh M (2021)

Publication Type: Journal article

Publication year: 2021

Journal

European Journal of Inorganic Chemistry Wiley-VCH Verlag

Book Volume: 2021

Pages Range: 567-577

Journal Issue: 6

DOI: 10.1002/ejic.202000954

Abstract

Five binuclear complexes with rectangular topology have been synthesized using a nitronyl-nitroxide ligand (L) functionalized with a pyrazole coordinating group: [Ln2(hfac)2L2], with Ln=Eu (1), Gd (2 a, 2 b), Tb (3), Dy (4), Tm (5). The Eu^III and Tm^III complexes crystallize in the P21/n space group, while the Gd^III, Tb^III, and Dy^III derivatives crystalize in P-1 space group. The crystal structures for compounds 2 a, 3, 4, and 5 have been fully solved, while for compounds 1 and 2 b, the unit cell parameters have been measured and compared with crystals 3 and 5. Crystals 2 a (P21/n) and 2 b (P-1) are polymorphic forms. In these complexes the nitronyl-nitroxide ligand bridges two metal ions through one aminoxyl group and the pyrazole fragment. In the five complexes the Ln^III ions show a coordination number of eight with a triangular dodecahedron geometry. The magnetic properties of all five complexes have been investigated. For compounds 2, 3, and 4 the Ln^III-Rad interaction was found to be ferromagnetic: JGdRad=2.09(1) cm⁻¹ [H=-2JGdRad(SGd1SRad1+SGd2SRad2], JTbRad=1.93(14) cm⁻¹, JDyRad=1.72(14) cm⁻¹. The Tm^III-Rad coupling is antiferromagnetic (JTmRad=−0.53(1) cm⁻¹). For the Tb^III, Dy^III, and Tm^III complexes the effects of the crystal field have been taken into account in the fitting procedure.

Involved external institutions

University of Bucharest / Universitatea din București

Romania (RO) Johannes Gutenberg-Universität Mainz (JGU)

Germany (DE) Moldova State University (MSU) / Universitatea de Stat din Moldova

Moldova, Republic of (MD) Fluminense Federal University / Universidade Federal Fluminense (UFF)

Brazil (BR)

How to cite

APA:

Calancea, S., Carrella, L., Mocanu, T., Sadohin, V., Raduca, M., Gutu, I.,... Andruh, M. (2021). Magnetic Molecular Rectangles Constructed from Functionalized Nitronyl-Nitroxide Ligands and Lanthanide(III) Ions. European Journal of Inorganic Chemistry, 2021(6), 567-577. https://dx.doi.org/10.1002/ejic.202000954

MLA:

Calancea, Sergiu, et al. "Magnetic Molecular Rectangles Constructed from Functionalized Nitronyl-Nitroxide Ligands and Lanthanide(III) Ions." European Journal of Inorganic Chemistry 2021.6 (2021): 567-577.

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