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Inorganics 2018, 6(1), 7;

Field-Induced Slow Magnetic Relaxation of Mono- and Dinuclear Dysprosium(III) Complexes Coordinated by a Chloranilate with Different Resonance Forms

Department of Chemistry, Faculty of Science, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, Sendai, Miyagi 980-8578, Japan
Advanced Institute for Materials Research (AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577, Japan
School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
Author to whom correspondence should be addressed.
Received: 14 November 2017 / Revised: 15 December 2017 / Accepted: 28 December 2017 / Published: 30 December 2017
(This article belongs to the Special Issue Single-Molecule Magnets)
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We synthesized the dinuclear and mononuclear dysprosium(III) complexes [{Dy(Tp)2}2(Cl2An)]·2CH2Cl2 (1) and [Co(Cp)2][Dy(Tp)2(Cl2An)] (3), where Cl2An2− and Tp are the chloranilate and hydrotris(pyrazolyl)borate ligand, respectively. In addition, the magnitude of the magnetic coupling between the lanthanide centers through the Cl2An2− bridge has been probed through the synthesis of [{Gd(Tp)2}2(Cl2An)]·2CH2Cl2 (2), which is a gadolinium(III) analogue of 1. Complexes 13 were characterized by infrared (IR) spectroscopy, elemental analysis, single-crystal X-ray diffraction, and SQUID measurements. IR and single-crystal X-ray structural analyses confirm that the coordination environments of the lanthanide(III) centers in 1 and 3 are similar to each other; i.e., eight-coordinated metal centers, each occupied by an N6O2 donor set from two Tp ligands and one Cl2An2− ligand. The coordination geometries of the lanthanide(III) centers in 1 and 2 are distorted triangular dodecahedral, while that in the mononuclear complex 3 is square antiprismatic, where the Cl2An2− ligand takes the bi-separated delocalized form in 1 and 2, and the o-quinone form in 3. Alternating-current (AC) magnetic studies clearly reveal that both 1 and 3 exhibit field-induced slow relaxations of magnetization that occur via Raman and direct processes. Complexes 1 and 3 exhibit different spin relaxation behavior, which reflects the coordination geometry around each DyIII center and its nuclearity, as well as the molecular packing in the crystal lattice. Although the magnetic analysis of 2 revealed negligible magnetic coupling, Cl2An2− bridges with small biases may form in the dinuclear complexes, which play roles in the spin relaxation dynamics through dipolar interactions. View Full-Text
Keywords: single-ion magnets; single-molecule magnets; lanthanide ions; slow magnetic relaxation single-ion magnets; single-molecule magnets; lanthanide ions; slow magnetic relaxation

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Ishikawa, R.; Michiwaki, S.; Noda, T.; Katoh, K.; Yamashita, M.; Matsubara, K.; Kawata, S. Field-Induced Slow Magnetic Relaxation of Mono- and Dinuclear Dysprosium(III) Complexes Coordinated by a Chloranilate with Different Resonance Forms. Inorganics 2018, 6, 7.

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