Field-induced single-ion magnet behaviors in 1-dimensionally assembled tetrahedral cobalt(II) complexes with halide donors

Mitsuhashi, Ryoji; Hosoya, Satoshi; Sunatsuki, Yukinari; Suzuki, Takayoshi; Mikuriya, Masahiro

doi:10.1016/j.ica.2021.120667

Cited by 3 publications

(3 citation statements)

References 35 publications

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“…Selected bond lengths and bond angles of 1 are given in Table S3 †. The Co(1)–N distances (2.001(1) and 2.008(2) Å) and the Co(1)–I distances (2.5946(2) and 2.5742(2) Å) are similar to the values obtained for tetrahedral cobalt( ii ) complexes with an N 2 I 2 coordination environment, 7 Table S1 †. The tetrahedral bond angles vary from 102.75(4) to 115.48(4)°.…”

Section: Resultssupporting

confidence: 67%

“…The zero field splitting (ZFS) parameter D describing the axial magnetic anisotropy is determined by the strength of the spin–orbit interaction and also by the ligand field around the Co ion, and so the D parameter may change in a wide range depending on the ligand environment. 1–3 Among different Co( ii ) complexes showing SIM behavior one can mention octahedral and quasi-octahedral Co( ii ) complexes, 2,4 linear complexes such as [(NHC)CoNDmp] and [Co(C(SiMe 2 ONaph) 3 ) 2 ] exhibiting the highest values of the magnetization reversal barrier ( U eff = 413 cm −1 and 450 cm −1 , respectively), 5 tetrahedral (or quasi-tetrahedral) complexes in which the D value varies from +20 cm −1 to −160 cm −1 depending on the ligand field symmetry and strength, 2,6,7 and trigonal prismatic complexes. 2,8 It is worth noting that octahedral, tetrahedral and trigonal prismatic complexes are stable, and from this point of view they are more attractive for practical use than the linear ones despite the fact that the latter complexes exhibit higher magnetic anisotropy.…”

Section: Introductionmentioning

confidence: 99%

“…The influence of halide ions (Cl, Br, or I) on the D value in a Co II L 2 Hal 2 series was also investigated. 7 Similar to the N, P, and As series, the effect of a heavy halogen atom is weak or even absent.…”

Section: Introductionmentioning

confidence: 99%

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Evidence for zero-field slow magnetic relaxation in a Co(ii) complex with a pseudo-tetrahedral N₂I₂ environment

et al. 2022

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Section: Resultssupporting

confidence: 67%

Section: Introductionmentioning

confidence: 99%

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Evidence for zero-field slow magnetic relaxation in a Co(ii) complex with a pseudo-tetrahedral N₂I₂ environment

et al. 2022

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Tuning Magnetic Anisotropy in Co(II) Tetrahedral Carbazole-Modified Phosphine Oxide Single-Ion Magnets: Importance of Structural Distortion versus Heavy-Ion Effect

Bhatt,

Sharma,

Gupta

et al. 2023

Inorg. Chem.

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Three mononuclear cobalt(II) tetrahedral complexes [Co(CzPh2PO)2X2] (CzPh2PO = (9H-carbazol-9-yl)diphenylphosphine oxide and X = Cl (1), Br (2), I (3)) have been synthesized using a simple synthetic approach to examine their single-ion magnetic (SIM) behavior. A detailed study of the variation in the dynamic magnetic properties of the Co(II) ion in a tetrahedral ligand field has been carried out by the change of the halide ligand. The axial zero-field splitting parameter D was found to vary from −16.4 cm–1 in 1 to −13.8 cm–1 in 2 and +14.6 cm–1 in 3. All the new complexes exhibit field-induced SIM behavior. The results obtained from ab initio CASSF calculations match well with the experimental data, revealing how halide ions induce a change in the D value as we move from Cl– to I–. The ab initio calculations further reveal that the change in the sign of D is due to the multideterminant characteristics of the ground state wave function of 1 and 2, while single-determinant characteristics are instead observed for 3. To gain a better understanding of the relationship between the structural distortion and the sign and magnitude of D values, magnetostructural D correlations were developed using angular relationships, revealing the importance of structural distortions over the heavy halide effect in controlling the sign of D values. This study broadens the scope of employing electronically and sterically modified phosphine oxide ligands in building new types of air-stable Co(II) SIMs.

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Slow Magnetic Relaxation in Cobalt(II) Complexes with One-Dimensional Hydrogen-Bonded Networks

Mitsuhashi

Sakiyama²,

Hayashi³

2023

Magnetochemistry

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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.

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Field-induced single-ion magnet behaviors in 1-dimensionally assembled tetrahedral cobalt(II) complexes with halide donors

Cited by 3 publications

References 35 publications

Evidence for zero-field slow magnetic relaxation in a Co(ii) complex with a pseudo-tetrahedral N₂I₂ environment

Evidence for zero-field slow magnetic relaxation in a Co(ii) complex with a pseudo-tetrahedral N₂I₂ environment

Tuning Magnetic Anisotropy in Co(II) Tetrahedral Carbazole-Modified Phosphine Oxide Single-Ion Magnets: Importance of Structural Distortion versus Heavy-Ion Effect

Slow Magnetic Relaxation in Cobalt(II) Complexes with One-Dimensional Hydrogen-Bonded Networks

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Field-induced single-ion magnet behaviors in 1-dimensionally assembled tetrahedral cobalt(II) complexes with halide donors

Cited by 3 publications

References 35 publications

Evidence for zero-field slow magnetic relaxation in a Co(ii) complex with a pseudo-tetrahedral N2I2 environment

Evidence for zero-field slow magnetic relaxation in a Co(ii) complex with a pseudo-tetrahedral N2I2 environment

Tuning Magnetic Anisotropy in Co(II) Tetrahedral Carbazole-Modified Phosphine Oxide Single-Ion Magnets: Importance of Structural Distortion versus Heavy-Ion Effect

Slow Magnetic Relaxation in Cobalt(II) Complexes with One-Dimensional Hydrogen-Bonded Networks

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Evidence for zero-field slow magnetic relaxation in a Co(ii) complex with a pseudo-tetrahedral N₂I₂ environment

Evidence for zero-field slow magnetic relaxation in a Co(ii) complex with a pseudo-tetrahedral N₂I₂ environment