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Syntheses, Structures and Magnetic Properties of Lanthanide Complexes of the Pyrimidyl-Substituted Nitronyl Nitroxide Radical

Abstract

Four 2p-4f Ln-Radical complexes, [(NIT-2-Pm)Ln(hfac)3]·0.5C7H16 (NIT-2-Pm = 2-pyrimidyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxy-3-oxide, hfac = hexafluoroacetylacetonato, Ln = Tb (1), Dy (2), Ho(3), Er (4)), and four 4f-2p-4f Ln-Radical-Ln complexes, [(μ-NIT-2-Pm)Ln2(hfac)6(H2O)2]·0.5C7H16 (Ln = Tb (5), Dy (6), Ho (7), Er (8)), have been synthesized and characterized structurally and magnetically. These compounds can be selectively obtained by controlling the reaction ratio of Ln(hfac)3·2H2O to the radical ligand NIT-2-Pm. The crystal structures show that in the former four complexes 1-4, the NIT-2-Pm radical acts as a terminal bidentate ligand chelating to one LnIII ion, while in 5-8, the NIT-2-Pm acts as a bridging ligand linking two LnIII ions to form a binuclear three-spins system. Magnetic studies revealed that complexes 1-4 and 6 show frequency-dependent ac magnetic susceptibilities, suggesting a possible single-molecule magnet behavior. To our best knowledge, complexes 3 and 4 are the first Ho-NIT and Er-NIT compounds showing the slow magnetic relaxation. Compounds 5-8 represent a rare family of compounds showing the NIT bridged 4f-2p-4f three-spins motif, while complex 6 is a rare NIT bridged multinuclear lanthanide compound possessing SMM-like behaviour. Ab initio calculations were performed on all these complexes.The fitting of the magnetic susceptibilities of these compounds suggests weak antiferromagnetic coupling between the LnIII and NIT radical in 1-8 and weak ferromagnetic LnIII-LnIII interactions in 5-8.

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Publication details

The article was received on 22 Mar 2017, accepted on 14 Jul 2017 and first published on 14 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT01037K
Citation: Dalton Trans., 2017, Accepted Manuscript
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    Syntheses, Structures and Magnetic Properties of Lanthanide Complexes of the Pyrimidyl-Substituted Nitronyl Nitroxide Radical

    J. Wang, H. Miao, Z. Xiao, Y. Zhou, L. Deng, Y. Zhang and X. Wang, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT01037K

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