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Magnetochemistry 2017, 3(1), 5; doi:10.3390/magnetochemistry3010005

Using the Singly Deprotonated Triethanolamine to Prepare Dinuclear Lanthanide(III) Complexes: Synthesis, Structural Characterization and Magnetic Studies

1
Department of Chemistry, University of Patras, 265 04 Patras, Greece
2
Departament de Química Inorgànica i Orgànica, Secció Inorgànica, and Institue of Nanoscience and Nanotechnology (IN2UB), Universitat de Barcelona, Av. Diagonal 645, 08028 Barcelona, Spain
3
Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 153 10 Aghia Paraskevi Attikis, Greece
4
Institute of Chemical Engineering Sciences, Foundation for Research and Technology-Hellas (FORTH/ICE-HT), Platani, P.O. Box 1414, 265 04 Patras, Greece
This article is dedicated to Dante Gatteschi, a pioneer in the interdisciplinary field of Molecular Magnetism and a great mentor, on the occasion of his 70th birthday.
*
Authors to whom correspondence should be addressed.
Academic Editor: Kevin Bernot
Received: 21 December 2016 / Revised: 13 January 2017 / Accepted: 16 January 2017 / Published: 26 January 2017
(This article belongs to the Special Issue Molecular Magnetism of Lanthanides Complexes and Networks)
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Abstract

The 1:1 reactions between hydrated lanthanide(III) nitrates and triethanolamine (teaH3) in MeOH, in the absence of external bases, have provided access to the dinuclear complexes [Ln2(NO3)4(teaH2)2] (Ln = Pr, 1; Ln = Gd, 2; Ln = Tb, 3; Ln = Dy, 4; Ln = Ho, 5) containing the singly deprotonated form of the ligand. Use of excess of the ligand in the same solvent gives mononuclear complexes containing the neutral ligand and the representative compound [Pr(NO3)(teaH3)2](NO3)2 (6) was characterized. The structures of the isomorphous complexes 1∙2MeOH, 2∙2MeOH and 4∙2MeOH were solved by single-crystal X-ray crystallography; the other two dinuclear complexes are proposed to be isostructural with 1, 2 and 4 based on elemental analyses, IR spectra and powder XRD patterns. The IR spectra of 16 are discussed in terms of structural features of the complexes. The two LnIII atoms in centrosymmetric 1∙2MeOH, 2∙2MeOH and 4∙2MeOH are doubly bridged by the deprotonated oxygen atoms of the two η11122 teaH2 ligands. The teaH2 nitrogen atom and six terminal oxygen atoms (two from the neutral hydroxyl groups of teaH2 and four from two slightly anisobidentate chelating nitrato groups) complete 9-coordination at each 4f-metal center. The coordination geometries of the metal ions are spherical-relaxed capped cubic (1∙2MeOH), Johnson tricapped trigonal prismatic (2∙2MeOH) and spherical capped square antiprismatic (4·2MeOH). O–H∙∙∙O H bonds create chains parallel to the a axis. The cation of 6 has crystallographic two fold symmetry and the rotation axis passes through the PrIII atom, the nitrogen atom of the coordinated nitrato group and the non-coordinated oxygen atom of the nitrato ligand. The metal ion is bound to the two η1111 teaH3 ligands and to one bidentate chelating nitrato group. The 10-coordinate PrIII atom has a sphenocoronal coordination geometry. Several H bonds are responsible for the formation of a 3D architecture in the crystal structure of 6. Complexes 16 are new members of a small family of homometallic LnIII complexes containing various forms of triethanolamine as ligands. Dc magnetic susceptibility studies in the 2–300 K range reveal the presence of a weak to moderate intramolecular antiferromagnetic exchange interaction (J = −0.30(2) cm−1 based on the spin Hamiltonian H ^ = - J ( S ^ Gd 1 S ^ Gd 1 ) ) for 2 and probably weak antiferromagnetic exchange interactions within the molecules of 35. The antiferromagnetic GdIII∙∙∙GdIII interaction in 2 is discussed in terms of known magnetostructural correlations for complexes possessing the {Gd22-OR)2}4+ core. Ac magnetic susceptibility measurements in zero dc field for 35 do not show frequency dependent out-of-phase signals; this experimental fact is discussed and rationalized for complex 4 in terms of the magnetic anisotropy axis for each DyIII center and the oblate electron density of the metal ion. View Full-Text
Keywords: dinuclear lanthanide(III) complexes; ground state magnetic axes of dysprosium(III) ions in a complex; magnetic properties; triethanolamine-lanthanide(III) complexes dinuclear lanthanide(III) complexes; ground state magnetic axes of dysprosium(III) ions in a complex; magnetic properties; triethanolamine-lanthanide(III) complexes
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MDPI and ACS Style

Mylonas-Margaritis, I.; Mayans, J.; Sakellakou, S.-M.; P. Raptopoulou, C.; Psycharis, V.; Escuer, A.; P. Perlepes, S. Using the Singly Deprotonated Triethanolamine to Prepare Dinuclear Lanthanide(III) Complexes: Synthesis, Structural Characterization and Magnetic Studies. Magnetochemistry 2017, 3, 5.

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