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Magnetic and Electrochemical Properties of Lantern-Type Dinuclear Ru(II,III) Complexes with Axial Chloride Ions or Water Molecules

1
Department of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
2
Department of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridaicho, Kita-Ku, Okayama 700-0005, Japan
3
Department of Science, Faculty of Science, Yamagata University, 1-4-12 Kojirakawa, Yamagata 990-8560, Japan
4
Department of Biological Sciences, Faculty of Science, Kanagawa University, Hiratsuka, Kanagawa 259-1293, Japan
5
Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda 669-1337, Japan
6
Research Institute of Natural Sciences, Okayama University of Science, 1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan
*
Authors to whom correspondence should be addressed.
Magnetochemistry 2019, 5(1), 18; https://doi.org/10.3390/magnetochemistry5010018
Received: 31 December 2018 / Revised: 22 February 2019 / Accepted: 25 February 2019 / Published: 6 March 2019
(This article belongs to the Special Issue Coordination Compounds for Coordination Molecule-Based Devices)
By using [Ru2(O2CC3H7)4Cl]n (1) as a starting material, nBu4N[Ru2(O2CC3H7)4Cl2] (nBu4N+ = tetra(n-butyl)ammonium cation) (2) and [Ru2(O2CC3H7)4(H2O)2]BF4 (3) were prepared. The lantern-type dinuclear structures with axial chloride ions or water molecules were confirmed for 2 and 3 by X-ray crystal structure analyses. The crystal structures of 2 and 3 were compared with that of 1. In the crystal of 2, there were three crystallographically different dinuclear units; the Ru–Ru distances of each unit were 2.3094(3), 2.3046(4), and 2.3034(4) Å, respectively, which were longer than those of 1 (2.281(4) Å) and 3 (2.2584 (7) Å). Temperature dependent magnetic susceptibility measurements were performed for 1 and 2 as well as 3. The effective magnetic moments (µeff) at 300 K were 3.97 (for 1), 4.00 (for 2), and 3.97 µB (for 3), respectively. The decreases in the µeff value were confirmed for all of the complexes due to the large zero-field splitting (D): D = 68 cm−1 for 1, 78 cm−1 for 2, and 60 cm−1 for 3. Cyclic voltammograms measured in CH2Cl2 with a electrolyte of nBu4N(BF4) showed the Ru25+/Ru24+ process at −0.2–−0.4 V (vs. SCE) and the Ru26+/Ru25+ one at 1.3–1.4 V (vs. SCE), of which potentials were confirmed by the DFT calculation for nBu4N[Ru2(O2CC3H7)4Cl2]. View Full-Text
Keywords: lantern-type diruthenium(II,III) complex; butanoato-bridge; crystal structures; magnetic properties; electrochemical properties; DFT calculation lantern-type diruthenium(II,III) complex; butanoato-bridge; crystal structures; magnetic properties; electrochemical properties; DFT calculation
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Handa, M.; Yairi, H.; Yano, N.; Mitsumi, M.; Sakiyama, H.; Kitashima, M.; Inoue, K.; Mitsuhashi, R.; Mikuriya, M.; Akashi, H.; Kataoka, Y. Magnetic and Electrochemical Properties of Lantern-Type Dinuclear Ru(II,III) Complexes with Axial Chloride Ions or Water Molecules. Magnetochemistry 2019, 5, 18.

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