<i>d</i>-Orbital orientation in a dimer cobalt complex: link to magnetic properties?

Deutsch, Maxime; Claiser, Nicolas; Gillet, Jean‐Michel; Lecomte, Claude; Sakiyama, Hiroshi; Tone, Katsuya; Sarwat, Mohamed

doi:10.1107/s0108768111022671

Cited by 11 publications

(7 citation statements)

References 24 publications

(26 reference statements)

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“…The high-spin Co(II) complexes exhibit excellent magnetic properties, which arise from the strong orbital angular momentum, such as several phenoxo-bridged cobalt(II) complexes behaving as single-molecule magnets. , Dinuclear complexes are suitable for investigating the magnetic interactions between paramagnetic centers transmitted through the phenoxo bridge because of their simple structures. , Over the past decades, a lot of reports have been made on dinuclear bis(μ-phenoxo)-bridged cobalt(II) complexes; in addition, most of them exhibit antiferromagnetic coupling (AF) between cobalt(II) centers, ,,− and only four cases show ferromagnetic coupling (F) between cobalt(II) centers. ,− To further understand the magnetic behavior of this system, more new μ-phenoxo-bridged Co(II) complexes need to be obtained and studied. Herein, we designed and synthesized a new Schiff-base ligand, (4-methyl-2-formyl-6-(((2-trifluoromethyl)phenyl)methyliminomethyl) phenol) (HL).…”

Section: Introductionmentioning

confidence: 99%

Study on the Magneto-Structural Correlation of a New Dinuclear Cobalt(II) Complex with Double μ-Phenoxo Bridges

Song

Xue

2020

ACS Omega

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A new μ-phenoxo-bridged dinuclear cobalt(II) complex, [Co2(L)2(acac)2(H2O)] (1), has been synthesized by employing a new ligand, (4-methyl-2-formyl-6-(((2-trifluoromethyl)phenyl)methyliminomethyl) phenol) (HL). Structural analysis of complex 1 reveals that the geometry around cobalt centers is best described as a distorted octahedron and the distance of cobalt neighbors is 3.128(0) Å. The magnetic property studies indicate that complex 1 exhibits strong spin–orbit coupling effects and weak ferromagnetic coupling between two high-spin Co(II) centers linked by double μ-Ophenoxo bridges, with J = 1.87(2) cm–1. The studies show that not only the Co–O–Co angle affects the alignment of the cobalt spins but also the dihedral angle between the CoOCo plane and the phenyl plane plays an important role in the magnetic coupling in this [Co2O2] system. Thus, the small bridging angles (96.96(11) and 96.91(11)°) and the large dihedral angles between the CoOCo plane and the phenyl plane (63.0(1) and 30.6(1)°) induce intramolecular ferromagnetic exchange interaction in complex 1.

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Section: Introductionmentioning

confidence: 99%

Study on the Magneto-Structural Correlation of a New Dinuclear Cobalt(II) Complex with Double μ-Phenoxo Bridges

Song

Xue

2020

ACS Omega

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“…The result is a list of d orbital occupancies that would generate the EDD around the Cu ion. This methodology has found application in diverse studies of magnetic properties and chemical bonding. − Critical herein is of course the occupancy of the d x 2 – y 2 orbital.…”

Section: Introductionmentioning

confidence: 99%

Experimental X-ray Electron Density Study of Atomic Charges, Oxidation States, and Inverted Ligand Field in Cu(CF₃)₄^–

2019

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The electron density distribution of the complex monoanion Cu(CF 3 ) 4 in (Bu 4 N)[Cu(CF 3 ) 4 ] has been studied by high-resolution X-ray single-crystal diffraction and augmented with theoretical calculations. The study finds that the central copper bears an atomic charge of close to +1, while the occupancy of its d x 2 −y 2 orbital is only 1.26. Using topological analysis combined with theoretical calculations, the depopulation of d x 2 −y 2 is shown to be due to significant covalency in the Cu−C bonds. The combination of the monovalent picture and the covalency is interpreted as a confirmation of an inverted ligand field.

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“…Crystal data are included in Table . The crystal structure of 2′ is isomorphous to that of a previous cobalt(II) complex. , The crystal consists of [Zn 2 ( sym -hmp) 2 ] 2+ complex cations, tetraphenylborate anions, acetone molecules, and water molecules in a 1:2:2:2 molar ratio. The structure of the complex cation is depicted in Figure .…”

Section: Resultsmentioning

confidence: 99%

Magnetic Properties of a Dinuclear Nickel(II) Complex with 2,6-Bis[(2-hydroxyethyl)methylaminomethyl]-4-methylphenolate

et al. 2016

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Magnetic properties of dinuclear nickel(II) complex [Ni(sym-hmp)](BPh)·3.5DMF·0.5(2-PrOH) (1), where (sym-hmp) is 2,6-bis[(2-hydroxyethyl)methylaminomethyl]-4-methylphenolate anion and DMF indicates dimethylformamide, were investigated using high-frequency and -field electron paramagnetic resonance (HFEPR). To magnetically characterize the mononuclear nickel(II) species forming the dimer, its two dinuclear zinc(II) analogues, [Zn(sym-hmp)](BPh)·3.5DMF·0.5(2-PrOH) (2) and [Zn(sym-hmp)](BPh)·2acetone·2HO (2'), were prepared. One of them (2') was structurally characterized by X-ray diffractometry and doped with 5% mol nickel(II) ions to prepare a mixed crystal 3. From the HFEPR results on complex 1 obtained at 40 K, the spin Hamiltonian parameters of the first excited spin state (S = 1) of the dimer were accurately determined as |D| = 9.99(2) cm, |E| = 1.62(1) cm, and g = [2.25(1), 2.19(2), 2.27(2)], and for the second excited spin state (S = 2) at 150 K estimated as |D| ≈ 3.5 cm. From these numbers, the single-ion zero-field splitting (ZFS) parameter of the Ni(II) ions forming the dimer was estimated as |D| ≈ 10-10.5 cm. The HFEPR spectra of 3 yielded directly the single-ion parameters for D = +10.1 cm, |E| = 3.1 cm, and g = 2.2. On the basis of the HFEPR results, the previously obtained magnetic data (Sakiyama, H.; Tone, K.; Yamasaki, M.; Mikuriya, M. Inorg. Chim. Acta 2011, 365, 183) were reanalyzed, and the isotropic interaction parameter between the Ni(II) ions was determined as J = -70 cm (H = -J S·S). Finally, density functional theory calculations yielded the J value of -90 cm in a qualitative agreement with the experiment.

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d-Orbital orientation in a dimer cobalt complex: link to magnetic properties?

Cited by 11 publications

References 24 publications

Study on the Magneto-Structural Correlation of a New Dinuclear Cobalt(II) Complex with Double μ-Phenoxo Bridges

Study on the Magneto-Structural Correlation of a New Dinuclear Cobalt(II) Complex with Double μ-Phenoxo Bridges

Experimental X-ray Electron Density Study of Atomic Charges, Oxidation States, and Inverted Ligand Field in Cu(CF₃)₄^–

Magnetic Properties of a Dinuclear Nickel(II) Complex with 2,6-Bis[(2-hydroxyethyl)methylaminomethyl]-4-methylphenolate

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d-Orbital orientation in a dimer cobalt complex: link to magnetic properties?

Cited by 11 publications

References 24 publications

Study on the Magneto-Structural Correlation of a New Dinuclear Cobalt(II) Complex with Double μ-Phenoxo Bridges

Study on the Magneto-Structural Correlation of a New Dinuclear Cobalt(II) Complex with Double μ-Phenoxo Bridges

Experimental X-ray Electron Density Study of Atomic Charges, Oxidation States, and Inverted Ligand Field in Cu(CF3)4–

Magnetic Properties of a Dinuclear Nickel(II) Complex with 2,6-Bis[(2-hydroxyethyl)methylaminomethyl]-4-methylphenolate

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Experimental X-ray Electron Density Study of Atomic Charges, Oxidation States, and Inverted Ligand Field in Cu(CF₃)₄^–