Coordination Compounds for Coordination Molecule-Based Devices

A special issue of Magnetochemistry (ISSN 2312-7481).

Deadline for manuscript submissions: closed (31 December 2018) | Viewed by 16952

Special Issue Editors


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Guest Editor
School of Science and Technology, Kwansei Gakuin University, 2-1 Sanda, 669-1337, Japan
Interests: coordination compounds; molecular magnetic compounds; coordination polymers; multifunctional materials

E-Mail Website
Guest Editor
Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
Interests: coordination compounds; molecular magnetic compounds; coordination polymers; multifunctional materials

Special Issue Information

Dear Colleagues,

Coordination chemistry has expanded into a very broad research area from physics to biology as well as pharmacology and has increased its importance in chemistry. Creating and developing new coordination compounds is indispensable. In this regard, it is not exaggerated to consider that all kinds of metal complexes can be a candidate for coordination molecule-based devices.

We invite all the researchers working with coordination compounds to submit their contributions to this Special Issue on any topics related to magnetic properties.

Prof. Dr. Masahiro Mikuriya
Prof. Dr. Makoto Handa
Guest Editors

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Keywords

  • magnetic properties
  • coordination compounds

Published Papers (6 papers)

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Research

13 pages, 3253 KiB  
Article
Magnetic and Electrochemical Properties of Lantern-Type Dinuclear Ru(II,III) Complexes with Axial Chloride Ions or Water Molecules
by Makoto Handa, Haruki Yairi, Natsumi Yano, Minoru Mitsumi, Hiroshi Sakiyama, Masaharu Kitashima, Kazuhito Inoue, Ryoji Mitsuhashi, Masahiro Mikuriya, Haruo Akashi and Yusuke Kataoka
Magnetochemistry 2019, 5(1), 18; https://doi.org/10.3390/magnetochemistry5010018 - 6 Mar 2019
Cited by 4 | Viewed by 2629
Abstract
By using [Ru2(O2CC3H7)4Cl]n (1) as a starting material, nBu4N[Ru2(O2CC3H7)4Cl2] (nBu4N+ [...] Read more.
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]. Full article
(This article belongs to the Special Issue Coordination Compounds for Coordination Molecule-Based Devices)
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10 pages, 642 KiB  
Article
Theoretical Equations of Zeeman Energy Levels for Distorted Metal Complexes with 3T1 Ground Terms
by Hiroshi Sakiyama
Magnetochemistry 2019, 5(1), 17; https://doi.org/10.3390/magnetochemistry5010017 - 3 Mar 2019
Cited by 3 | Viewed by 2566
Abstract
The theoretical equations of Zeeman energy levels, including the zero-field energies and the first- and second-order Zeeman coefficients, have been obtained in closed form for nine states of the 3 T 1 ( g ) ground term, considering the axial ligand-field splitting and [...] Read more.
The theoretical equations of Zeeman energy levels, including the zero-field energies and the first- and second-order Zeeman coefficients, have been obtained in closed form for nine states of the 3 T 1 ( g ) ground term, considering the axial ligand-field splitting and the spin-orbit coupling. The equations are expressed as the functions of three independent parameters, Δ , λ , and κ , where Δ is the axial ligand-field splitting parameter, λ is the spin-orbit coupling parameter, and κ is the effective orbital reduction factor, including the admixing. The equations are useful in simulating magnetic properties (magnetic susceptibility and magnetization) of the complexes with 3 T 1 ( g ) ground terms, e.g., octahedral vanadium(III), octahedral low-spin manganese(III), octahedral low-spin chromium(II), and tetrahedral nickel(II) complexes. Full article
(This article belongs to the Special Issue Coordination Compounds for Coordination Molecule-Based Devices)
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11 pages, 2340 KiB  
Article
Tetranuclear Hetro-Metal [MnIII2NiII2] Complexes Involving Defective Double-Cubane Structure: Synthesis, Crystal Structures, and Magnetic Properties
by Yuki Suemitsu, Ryuji Matsunaga, Takashi Toyofuku, Yasunori Yamada, Masahiro Mikuriya, Tadashi Tokii and Masayuki Koikawa
Magnetochemistry 2019, 5(1), 14; https://doi.org/10.3390/magnetochemistry5010014 - 14 Feb 2019
Cited by 2 | Viewed by 2663
Abstract
Tetranuclear hetero-metal MnIII2NiII2 complexes, [Mn2Ni2(L)4(OAc)2] (1) and [Mn2Ni2(L)4(NO3)2] (2) [H2L = N-(2-hydroxymethylphenyl)-5,6-benzosalicylideneimine], have [...] Read more.
Tetranuclear hetero-metal MnIII2NiII2 complexes, [Mn2Ni2(L)4(OAc)2] (1) and [Mn2Ni2(L)4(NO3)2] (2) [H2L = N-(2-hydroxymethylphenyl)-5,6-benzosalicylideneimine], have been synthesized and characterized by X-ray crystal structure analyses, infrared spectra, and elemental analyses. The structure analyses revealed that the complexes have a defective double-cubane metal core connected by μ3-alkoxo bridges. Complexes consist of two bis-μ-alkoxo bridged MnIIINiII heteronuclear units making a dimer-of-dimers structure. The double-cubane cores are significantly distorted due to an effect of syn–syn mode acetato or nitrato bridges. Magnetic measurements indicate that weak antiferromagnetic interactions (Mn-Ni = −0.66 ~ −4.19 cm–1) are dominant in the hetero-metal core. Full article
(This article belongs to the Special Issue Coordination Compounds for Coordination Molecule-Based Devices)
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13 pages, 3123 KiB  
Article
High-temperature Spin Crossover of a Solvent-Free Iron(II) Complex with the Linear Hexadentate Ligand [Fe(L2-3-2Ph)](AsF6)2 (L2-3-2Ph = bis[N-(1-Phenyl-1H-1,2,3-triazol-4-yl)methylidene-2-aminoethyl]-1,3-propanediamine)
by Hiroaki Hagiwara
Magnetochemistry 2019, 5(1), 10; https://doi.org/10.3390/magnetochemistry5010010 - 1 Feb 2019
Cited by 2 | Viewed by 3383
Abstract
A novel mononuclear iron(II) complex with a linear hexadentate N6 ligand, containing two 1,2,3-triazole moieties, [Fe(L2-3-2Ph)](AsF6)2 (1), was synthesized (L2-3-2Ph = bis[N-(1-Phenyl-1H-1,2,3-triazol-4-yl)methylidene-2-aminoethyl]-1,3-propanediamine). Variable-temperature magnetic susceptibility measurements revealed a [...] Read more.
A novel mononuclear iron(II) complex with a linear hexadentate N6 ligand, containing two 1,2,3-triazole moieties, [Fe(L2-3-2Ph)](AsF6)2 (1), was synthesized (L2-3-2Ph = bis[N-(1-Phenyl-1H-1,2,3-triazol-4-yl)methylidene-2-aminoethyl]-1,3-propanediamine). Variable-temperature magnetic susceptibility measurements revealed a gradual one-step spin crossover (SCO) between the high-spin (HS, S = 2) and low-spin (LS, S = 0) states above room temperature (T1/2 = 468 K). The spin transition was further confirmed by differential scanning calorimetry (DSC). A single-crystal X-ray diffraction study showed that the complex was in the LS state (S = 0) at room temperature (296 K). In the crystal lattice, a three-dimensional (3D) supramolecular network was formed by intermolecular CH⋯π and π–π interactions of neighboring complex cations [Fe(L2-3-2Ph)]2+. AsF6 ions were located interstitially in the 3D network of complex cations, with no solvent-accessible voids. The crystal structure at 448 K (mixture of HS and LS species) was also successfully determined thanks to the thermal stability of the solvent-free crystal. Full article
(This article belongs to the Special Issue Coordination Compounds for Coordination Molecule-Based Devices)
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13 pages, 3625 KiB  
Article
Synthesis, Crystal Structures, and Magnetic Properties of Mixed-Valent Tetranuclear Complexes with Y-Shaped MnII2MnIII2 Core
by Masahiro Mikuriya, Satoshi Kurahashi, Seiki Tomohara, Yoshiki Koyama, Daisuke Yoshioka, Ryoji Mitsuhashi and Hiroshi Sakiyama
Magnetochemistry 2019, 5(1), 8; https://doi.org/10.3390/magnetochemistry5010008 - 28 Jan 2019
Cited by 8 | Viewed by 2419
Abstract
Tetranuclear MnII2MnIII2 complexes with 1,3-bis(5-bromo-3-metoxysalicylidenaminomethyl)-2-propanol (H3bmsap) and 1,3-bis(5-chloro-3-methoxysalicylidenaminomethyl)-2-propanol (H3cmsap), [Mn4(bmsap)2(CH3CO2)3(CH3O)] (3) and [Mn4(cmsap)2(CH3CO2 [...] Read more.
Tetranuclear MnII2MnIII2 complexes with 1,3-bis(5-bromo-3-metoxysalicylidenaminomethyl)-2-propanol (H3bmsap) and 1,3-bis(5-chloro-3-methoxysalicylidenaminomethyl)-2-propanol (H3cmsap), [Mn4(bmsap)2(CH3CO2)3(CH3O)] (3) and [Mn4(cmsap)2(CH3CO2)3(CH3O)] (4), were synthesized and characterized by elemental analysis, infrared and diffused reflectance spectra and variable-temperature magnetic susceptibility measurements in the 2–300 K range. The crystal structures of 3 and 4 revealed a Y-shaped tetranuclear manganese cluster formed by the two Schiff-base ligands, three kinds of acetato ligands (bidentate, syn–anti-bridging, and syn–syn-bridging), and µ-methoxido ligand. The magnetic data showed the magnetic interactions among the four manganese atoms are antiferromagnetic as a whole within the tetranuclear cluster. Full article
(This article belongs to the Special Issue Coordination Compounds for Coordination Molecule-Based Devices)
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8 pages, 2200 KiB  
Article
Stepwise Synthesis, Hydrogen-Bonded Supramolecular Structure, and Magnetic Property of a Co–Mn Heterodinuclear Complex
by Ryoji Mitsuhashi, Takaaki Ueda and Masahiro Mikuriya
Magnetochemistry 2019, 5(1), 5; https://doi.org/10.3390/magnetochemistry5010005 - 20 Jan 2019
Cited by 2 | Viewed by 2875
Abstract
A cobalt(III)–manganese(II) heterometallic dinuclear complex, [MnII{CoIII(µ-Himn)3}Cl2(CH3OH)], was prepared by a metalloligand approach. X-ray crystallographic analysis indicated that the metalloligand [CoIII(Himn)3] underwent mer/fac geometrical isomerization upon coordination to a Mn [...] Read more.
A cobalt(III)–manganese(II) heterometallic dinuclear complex, [MnII{CoIII(µ-Himn)3}Cl2(CH3OH)], was prepared by a metalloligand approach. X-ray crystallographic analysis indicated that the metalloligand [CoIII(Himn)3] underwent mer/fac geometrical isomerization upon coordination to a Mn ion. Owing to the non-coordinating N–H bonds in the [CoIII(Himn)3] moiety, the heterodinuclear complex exhibited hydrogen bond interactions with the Cl ligand of the neighboring complex to construct two-dimensional hydrogen-bond networks. The bond distances around the Mn center and the χMT value at 300 K indicate that the Mn center is in a divalent state. The temperature dependence of the χMT product and field dependence of the magnetization showed the isotropic nature of the MnII center. Full article
(This article belongs to the Special Issue Coordination Compounds for Coordination Molecule-Based Devices)
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