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Magnetochemistry
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Characterization of Coordination Compounds
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Characterization of Coordination Compounds

A special issue of Magnetochemistry (ISSN 2312-7481). This special issue belongs to the section "Magnetic Materials".

Deadline for manuscript submissions: closed (30 September 2022) | Viewed by 16278

Special Issue Editor

Prof. Dr. Salah Massoud

E-Mail Website
Guest Editor
1. Department of Chemistry, University of Louisiana at Lafayette, P.O. Box 43700, Lafayette, LA 70504, USA
2. Department of Chemistry, Faculty of Science, Alexandria University, Moharam Bey, Alexandria 21511, Egypt
Interests: bioinorganic chemistry; polynuclear transition metal complexes; lanthanides; fluorescence; molecular magnetism; SMMs and SIMs
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Coordination chemistry is a wide branch of inorganic chemistry. In the design of coordination compounds, several crucial points should be considered for successful synthesis of the target molecule. These include the electronic nature of the central metal ion, its oxidation state, the kind of inorganic salt used, the skeletal nature of the coordinating ligands and donor atoms, the steric effect which may or may not be encountered in the ligands’ structures and the nature of other anions in solutions which may have a tendency to assemble and link metal centers to form polynuclear species and/or coordination polymers. However, still the most important issue in the design of coordination compounds is their utility and/or potential applications. Therefore, the fascinating chemical, topological and physical properties of the coordination compounds have made them the central focus of extensive research in chemistry and in the multidisciplinary fields. The applications of these compounds extend to many aspects of life science and medical fields (pharmaceutical drugs, anticancer agents, electron transfer reactions, models to mimic biological molecules, metalloproteins, oxygen carrier molecules, MRI), material sciences (coordination polymers, sensors, MOFs, nanoparticles, molecular electronics, electrical conductivity, luminescence emission spectroscopy), industry (metallurgy, homogeneous catalysis, polymerization, pigments) and molecular magnetism (magnetic properties of coordination compounds in general, SMMs, SIMs, spin crossover). In addition to the traditional physicochemical methods used for characterization of the synthesized coordination compounds, some methods depend on the electronic nature of the central metal ion, such as magnetism. Following all of the above, we invite investigators to submit papers to this Special Issue entitled "Characterization of Coordination Compounds” in Magnetochemistry. This Special Issue is devoted to the synthesis and characterization of this class of compounds, where the magnetic properties are used as one of the structural analysis techniques.   

Prof. Dr. Salah Massoud
Guest Editor

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Keywords

  • Coordination compounds
  • Magnetic properties
  • Spin crossover
  • Single-molecule magnets (SMMs)
  • Single-ion magnets (SIMs)
  • Spectroscopic methods
  • Coordination polymers
  • Polynuclear coordination compounds
  • Bridged coordination compounds
  • Bio-coordination compounds
  • Coordination compounds as catalysts
  • Luminescence emission
  • Lanthanides
  • Actinides
  • Supramolecular coordination compounds
  • Photochemistry of coordination compounds
  • Crystal engineering
  • DFT calculations

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Published Papers (7 papers)

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Research

11 pages, 7088 KiB  
Article
Slow Magnetic Relaxation in Cobalt(II) Complexes with One-Dimensional Hydrogen-Bonded Networks
by Ryoji Mitsuhashi, Hiroshi Sakiyama and Yoshihito Hayashi
Magnetochemistry 2023, 9(1), 17; https://doi.org/10.3390/magnetochemistry9010017 - 1 Jan 2023
Viewed by 1802
Abstract
Two new cobalt(II) complexes with an unsymmetrical bidentate ligand, 2-(1,4,5,6-tetrahydropyrimidin-2-yl)-6-methoxyphenol (H2mthp), were synthesized and crystallographically characterized. Tetra- and hexa-coordinate mononuclear complexes were selectively obtained by adjusting the stoichiometry of the base. The coordination geometry of hexa-coordinated complex was severely distorted from [...] Read more.
Two new cobalt(II) complexes with an unsymmetrical bidentate ligand, 2-(1,4,5,6-tetrahydropyrimidin-2-yl)-6-methoxyphenol (H2mthp), were synthesized and crystallographically characterized. Tetra- and hexa-coordinate mononuclear complexes were selectively obtained by adjusting the stoichiometry of the base. The coordination geometry of hexa-coordinated complex was severely distorted from an ideal octahedron, due to the NO5 coordination environment from the mixed coordination of one Hmthp− and two H2mthp ligands. Both complexes formed one-dimensional chain networks by hydrogen-bond and N-H···π interactions. Single-molecule magnet behavior was observed for the tetrahedral complex under zero magnetic field. The relatively short Co···Co distances induced non-zero intermolecular magnetic coupling, which split the ground ±Ms levels to suppress quantum-tunneling of magnetization. In the octahedral complex, by contrast, the distance was not short enough to induce the coupling. As a consequence, single-molecule magnetic behavior was observed for the octahedral complex only in the presence of an external static field. Full article
(This article belongs to the Special Issue Characterization of Coordination Compounds)
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12 pages, 2818 KiB  
Article
Crystal Structures and Magnetic Properties of Diaquatetrapyridinenickel(II) and Diaquatetrapyridinecobalt(II) Complexes
by Hiroshi Sakiyama, Yuya Yamamoto, Ryusei Hoshikawa and Ryoji Mitsuhashi
Magnetochemistry 2023, 9(1), 14; https://doi.org/10.3390/magnetochemistry9010014 - 30 Dec 2022
Cited by 2 | Viewed by 1692
Abstract
Metal complexes with pyridine ligands (py) have not been crystallographically characterized in large numbers, while a large number of 2,2′-bipyridine (bpy) complexes have been structurally characterized. Against this background of scarcity of py complexes, the aim of this study was to characterize the [...] Read more.
Metal complexes with pyridine ligands (py) have not been crystallographically characterized in large numbers, while a large number of 2,2′-bipyridine (bpy) complexes have been structurally characterized. Against this background of scarcity of py complexes, the aim of this study was to characterize the structures and magnetic properties of complexes with pyridine ligands. In this study, new py complexes, trans-[Ni(H2O)2(py)4][BPh4]2·4py (1) and trans-[Co(H2O)2(py)4][BPh4]2·4py (2), were prepared and characterized by the single-crystal X-ray diffraction method and magnetic measurements. In the crystal structure analysis, both complexes were found to have octahedral trans-N2O4 coordination geometry, and the coordination of the trans-aqua ligands was found to be enhanced by the hydrogen-bonded pyridine molecules as a base. In the simultaneous analysis of magnetic susceptibility and magnetization, both complexes were found to show strong magnetism in one direction (χz > χx, χy; Mz > Mx, My), and this was explained by the enhancement of the axial aqua ligands. In the nickel(II) complex, the strong axial ligand field was found to cause negative zero-field splitting (D < 0) to show the magnetic behavior, while in the cobalt(II) complex, the strong axial π-orbital effect was found to cause negative ligand field splitting (Δ) in the 4T1 ground state to show the magnetic behavior. Full article
(This article belongs to the Special Issue Characterization of Coordination Compounds)
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16 pages, 1580 KiB  
Article
Magnetic and Luminescence Properties of 8-Coordinated Pyridyl Adducts of Samarium(III) Complexes Containing 4,4,4-Trifluoro-1-(naphthalen-2-yl)-1,3-butanedionate
by Franz A. Mautner, Florian Bierbaumer, Ramon Vicente, Saskia Speed, Ánnia Tubau, Roland C. Fischer and Salah S. Massoud
Magnetochemistry 2022, 8(7), 72; https://doi.org/10.3390/magnetochemistry8070072 - 11 Jul 2022
Cited by 5 | Viewed by 2069
Abstract
A novel series of polypyridyl adducts, [Sm(ntfa)3(NN)] (2–4), with ntfa = 4,4,4-trifluoro-1-(naphthalen-2-yl)-1,3-butanedionate, NN = 2,2′-bipyridine (bipy), 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me2bipy), and 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me2bipy) were synthesized from the precursor complex [Sm(ntfa)3(MeOH)2] ( [...] Read more.
A novel series of polypyridyl adducts, [Sm(ntfa)3(NN)] (2–4), with ntfa = 4,4,4-trifluoro-1-(naphthalen-2-yl)-1,3-butanedionate, NN = 2,2′-bipyridine (bipy), 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me2bipy), and 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me2bipy) were synthesized from the precursor complex [Sm(ntfa)3(MeOH)2] (1) and the corresponding pyridyl ligands. Single X-ray crystallography showed that the complexes displayed 8-coordinated geometry. The solid pyridyl adducts 2–4 exhibited emission of luminescence in the NIR and visible regions with close quantum yields (QY = 0.20–0.25%). The magnetic data of 1–4 showed larger values than those expected for magnetically noncoupled Sm(III) complexes in the 6H5/2 ground state, with no saturation on the applied high magnetic field static at a temperature of 2 K. Full article
(This article belongs to the Special Issue Characterization of Coordination Compounds)
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14 pages, 3331 KiB  
Article
Heterometallic Chain Compounds of Tetrakis(µ-carboxylato)diruthenium and Tetracyanidoaurate
by Masahiro Mikuriya, Yusuke Tanaka, Daisuke Yoshioka, Motohiro Tsuboi, Hidekazu Tanaka and Makoto Handa
Magnetochemistry 2022, 8(5), 48; https://doi.org/10.3390/magnetochemistry8050048 - 2 May 2022
Cited by 2 | Viewed by 2177
Abstract
Heterometallic complexes of tetrakis(µ-carboxylato)diruthenium(II,III) with tetracyanidoaurate(III) [Ru2(RCOO)4Au(CN)4]n (R = CH3 (1), C2H5 (2), i-C3H7 (3), and t-C4H9 ( [...] Read more.
Heterometallic complexes of tetrakis(µ-carboxylato)diruthenium(II,III) with tetracyanidoaurate(III) [Ru2(RCOO)4Au(CN)4]n (R = CH3 (1), C2H5 (2), i-C3H7 (3), and t-C4H9 (4)) were synthesized and characterized by C,H,N-elemental analysis and infrared spectroscopy and diffuse reflectance spectroscopy. The molecular structures were determined by a single-crystal X-ray diffraction method. A polymeric arrangement with the Ru2(RCOO)4+ units alternately linked by Au(CN)4− units is formed in these complexes. The trans-bridging mode of the Au(CN)4− unit for connecting the two Ru2(RCOO)4+ units was observed for 1 and 4, while the cis-bridging mode of the Au(CN)4− unit was observed for 2 and 3. Magnetic susceptibility data with variable temperature were modeled with a zero-field splitting model (D = 75 cm−1) and the presence of weak antiferromagnetic coupling between the RuIIRuIII units (zJ = −0.15~−0.10 cm−1) was estimated. N2-adsorption isotherms showed Type II curves with SBET of 0.728–2.91 m2 g−1. Full article
(This article belongs to the Special Issue Characterization of Coordination Compounds)
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18 pages, 5081 KiB  
Article
Structures and Properties of 4-phpy, pyz, and 4,4′-bpy Adducts of Lantern-Type Dirhodium Complexes with µ-Formamidinato and µ-Carboxylato Bridges
by Makoto Handa, Satoshi Nishiura, Makoto Kano, Natsumi Yano, Haruo Akashi, Masahiro Mikuriya, Hidekazu Tanaka, Tatsuya Kawamoto and Yusuke Kataoka
Magnetochemistry 2021, 7(3), 39; https://doi.org/10.3390/magnetochemistry7030039 - 15 Mar 2021
Cited by 2 | Viewed by 2480
Abstract
Dinuclear and polymer complexes of 4-phenylpyridine (4-phpy), pyazine (pyz), and 4,4′-bipyridine (4,4′-bpy) were prepared by using cis-[Rh2(4-Me-pf)2(O2CR)2] (4-Me-pf- =N,N’-bis(4-methylphenyl)formamidinate anion; R = CF3 and CMe3) as precursor dinuclear [...] Read more.
Dinuclear and polymer complexes of 4-phenylpyridine (4-phpy), pyazine (pyz), and 4,4′-bipyridine (4,4′-bpy) were prepared by using cis-[Rh2(4-Me-pf)2(O2CR)2] (4-Me-pf- =N,N’-bis(4-methylphenyl)formamidinate anion; R = CF3 and CMe3) as precursor dinuclear units. The dinuclear structures of cis-[Rh2II,II(4-Me-pf)2(O2CR)2(4-phpy)2] and cis-[Rh2II,III(4-Me-pf)2(O2CCMe3)2(4-phpy)2]BF4 and polymer structures of [Rh2II,II(4-Me-pf)2(O2CR)2(L)]n (L = pyz and 4,4′-bpy) were confirmed by X-ray crystal structure analyses. In these complexes, the lantern-type dinuclear core structures with cis-(2:2) arrangement of formamidinato (4-Me-pf-) and carboxylato ligands are preserved with Rh–Rh distances of 2.44–2.47 Å, regardless of the difference in the axial ligand and oxidation state Rh2II,II or Rh2II,III. In the cyclic voltammograms (CVs) in CH2Cl2, the redox potentials for Rh2II,III/Rh2II,II were estimated as E1/2 = 0.07 V and −0.28 V (vs. Fc+/Fc) for cis-[Rh2(4-Me-pf)2(O2CCF3)2(4-phpy)2] and cis-[Rh2(4-Me-pf)2(O2CCMe3)2(4-phpy)2], respectively, negatively shifted by 0.16 and 0.12 V compared with those of corresponding parent dinuclear complexes. The results were interpreted that the axial interaction with 4-phpy ligands makes the Rh2II,II core oxidized easily. The oxidized complex cis-[Rh2(4-Me-pf)2(O2CCMe3)2(4-phpy)2]BF4 is paramagnetic, which was confirmed by effective magnetic moment value μeff = 1.90 μB at 300 K per Rh2II,III unit (S = 1/2). The polymer complexes [Rh2(4-Me-pf)2(O2CR)2(L)]n (L = pyz and 4,4′-bpy) showed Type II gas-adsorption properties for N2. Full article
(This article belongs to the Special Issue Characterization of Coordination Compounds)
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13 pages, 4336 KiB  
Article
Copper(II) Carboxylates with 2,3,4-Trimethoxybenzoate and 2,4,6-Trimethoxybenzoate: Dinuclear Cu(II) Cluster and µ-Aqua-Bridged Cu(II) Chain Molecule
by Masahiro Mikuriya, Chihiro Yamakawa, Kensuke Tanabe, Raigo Nukita, Yuki Amabe, Daisuke Yoshioka, Ryoji Mitsuhashi, Ryota Tatehata, Hidekazu Tanaka, Makoto Handa and Motohiro Tsuboi
Magnetochemistry 2021, 7(3), 35; https://doi.org/10.3390/magnetochemistry7030035 - 8 Mar 2021
Cited by 13 | Viewed by 2915
Abstract
Copper(II) complexes with 2,3,4-trimethoxybenzoic acid (H234-tmbz) and 2,4,6-trimethoxybenzoic acid (H246-tmbz), [Cu2(234-tmbz)4(H2O)2] (6) and [Cu(246-tmbz)2(µ-H2O)2(H2O)2]n (7), were synthesized and characterized by [...] Read more.
Copper(II) complexes with 2,3,4-trimethoxybenzoic acid (H234-tmbz) and 2,4,6-trimethoxybenzoic acid (H246-tmbz), [Cu2(234-tmbz)4(H2O)2] (6) and [Cu(246-tmbz)2(µ-H2O)2(H2O)2]n (7), were synthesized and characterized by elemental analysis, infrared and UV-vis spectra and temperature dependence of magnetic susceptibilities (1.9–300 K). The X-ray crystal structures revealed that the former 6 is a dinuclear cluster having syn-syn-bridged Cu2(µ-234-tmbz)4 core with Cu···Cu separation of 2.6009(7) Å, while the latter 7 is a µ-aqua-bridged chain molecule consisting of Cu(246-tmb)2(µ-H2O)2(H2O)2 units with Cu···Cu separation of 4.1420(5) Å. Temperature dependence of magnetic susceptibilities showed that an antiferromagnetic interaction with 2J = −272 cm−1 for 6 and a weak antiferromagnetic interaction with J = −0.21 cm−1 for 7, between the two copper(II) ions. The adsorption isotherm of 6 showed Types I behavior having a 125.4 m2g−1 of specific surface area. Full article
(This article belongs to the Special Issue Characterization of Coordination Compounds)
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11 pages, 1881 KiB  
Article
Magneto-Structural Relationship of Tetragonally-Compressed Octahedral Iron(II) Complex Surrounded by a pseudo-S6 Symmetric Hexakis-Dimethylsulfoxide Environment
by Hiroshi Sakiyama, Takaaki Abiko, Masayuki Koikawa and Mikio Yamasaki
Magnetochemistry 2021, 7(2), 30; https://doi.org/10.3390/magnetochemistry7020030 - 23 Feb 2021
Cited by 1 | Viewed by 2041
Abstract
Since the octahedral high-spin iron(II) complex has the 5T2g ground term, the spin-orbit coupling should be considered in magnetic analysis; however, such treatment is rarely seen in recent papers, although the symmetry-sensitive property is of interest to investigate in detail. [...] Read more.
Since the octahedral high-spin iron(II) complex has the 5T2g ground term, the spin-orbit coupling should be considered in magnetic analysis; however, such treatment is rarely seen in recent papers, although the symmetry-sensitive property is of interest to investigate in detail. A method to consider the T-term magnetism was well constructed more than half a century ago. On the other hand, the method has been still improved in recent years. In this study, the octahedral high-spin iron(II) complex [Fe(dmso)6][BPh4]2 (dmso: dimethylsulfoxide) was newly prepared, and the single-crystal X-ray diffraction method revealed the tetragonal compression of the D4-symmetric coordination geometry around the iron(II) ion and the pseudo-S6 hexakis-dmso environment. From the magnetic data, the sign of the axial splitting parameter, Δ, was found to be negative, indicating the 5E ground state in the D4 symmetry. The DFT computation showed the electronic configuration of (dxz)2(dx2−y2)1(dyz)1(dxy)1(dz2)1 due to the tetragonal compression and the pseudo-S6 environment of dmso π orbitals. The electronic configuration corresponded to the 5E ground term, which was in agreement with the negative Δ value. Therefore, the structurally predicted ground state was consistent with the estimation from the magnetic measurements. Full article
(This article belongs to the Special Issue Characterization of Coordination Compounds)
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