Synthesis, Crystal Structures and Magnetic Properties of Two Heterobridged µ‐Phenoxo‐µ<sub>1,1</sub>‐Azide/Isocyanate Dinickel(II) Compounds: Experimental and Theoretical Exploration

Mandal, Shuvankar; Majumder, Samit; Mondal, Suraj; Mohanta, Sasankasekhar

doi:10.1002/ejic.201800742

Cited by 12 publications

(6 citation statements)

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“…As far the values of the intramolecular magnetic interactions in 2–5 are concerned, the lack of previous magneto‐structural studies on these type of heterobridged motifs with high‐spin cobalt(II) ions precludes any comparison. Anyway, the antiferromagnetic coupling found for 2 ( J = –4.19 cm –1 ) is in line with that obtained for the related isostructural trinickel(II) derivative ( J = – 24.8 cm –1 for 1 ) and the ferromagnetic interactions observed for 4 ( J = +10.9 cm –1 ) and 5 ( J = +0.07 cm –1 ) are also what one could expect having in mind the ferromagnetic couplings reported for the related µ ‐phenoxido‐µ 1,1 ‐pseudohalide dinickel(II) complexes …”

Section: Resultssupporting

confidence: 88%

“…Anyway, the antiferromagnetic coupling found for 2 (J = -4.19 cm -1 ) is in line with that obtained for the related isostructural trinickel(II) derivative (J = -24.8 cm -1 for 1) and the ferromagnetic interactions observed for 4 (J = +10.9 cm -1 ) and 5 (J = +0.07 cm -1 ) are also what one could expect having in mind the ferromagnetic couplings reported for the related μ-phenoxido-μ 1,1 -pseudohalide dinickel(II) complexes. [14] Alternatively, the magnetic data of 2-5 can be described by the phenomenological approach based on the zfs of a S = 3/2 through the spin Hamiltonian of Equation ( 3):…”

Section: Spectral and Magnetic Propertiesmentioning

confidence: 99%

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Trinuclear Nickel(II) and Cobalt(II) Complexes Constructed from Mannich–Schiff‐Base Ligands: Synthesis, Crystal Structures, and Magnetic Properties

et al. 2019

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Trinuclear Co II and Ni II complexes have been assembled using an octadentate Mannich-Schiff-base proligand H 2 L 2 which is obtained by reacting the Mannich base HL 1 with propylenediamine (2:1 molar ratio). HL 1 is obtained from 5bromo-salicylaldehyde and N,N,N′-trimethyl-ethylenediamine. The reaction of H 2 L 2 with nickel(II) and cobalt(II) as nitrate salts affords the trinuclear complexes [Ni 3 (L 2 )(NO 3 ) 4 ]·CH 3 CN (1) and [Co 3 (L 2 )(NO 3 ) 4 ]·CH 3 CN (2) in which the metal ions are bridged by one phenoxido and a nitrato-oxygen atoms. Within each complex, two of the four nitrato groups act as chelating ligands against the terminal metal ions. The central metal ions in 1 and 3 ) 2 ]· 2CH 3 CN (5). The magnetic properties of the five compounds have been investigated, revealing the occurrence on intramolecular antiferro-(1 and 2) and ferromagnetic interactions (3, 4 and 5). The nature and size of these interactions are discussed and compared to previously reported results on related systems.Scheme 1. Macrocyclic (A) and end-off (B) compartmental proligands nation environments. Such complexes have relevance in molecular magnetism, [3] biomimetic inorganic chemistry, [4] and catalysis. [5] Using 5-substituted salicylaldehydes as a platform for Mannich and Schiff reactions, the sizes of the two compartments can be tuned by choosing amine precursors with various Scheme 2. Dissymmetric proligands Full Paper numbers of carbon atoms. Moreover, the two amines can contain additional coordinating groups. Other proligands obtained following this strategy are potentially tetradentate and contain only one compartment, Mannich or Schiff (see Scheme 2). These organic molecules can generate not only binuclear complexes, but also high nuclearity clusters. [6] In this paper we report on new trinuclear complexes which are aggregated using an octadentate Schiff-Mannich base ligand featuring a salen-like moiety. Their syntheses, crystal structures and magnetic properties are discussed. Results and DiscussionThe new ligand has been obtained starting from 5-bromosalicylaldehyde: in the first step, the Mannich reaction leads to the intermediate HL 1 species (see Scheme 3); [7] in the second step, the octadentate ligand H 2 L 2 is obtained by reacting HL 1 with propylenediamine (2:1 molar ratio). This last reaction occurs in situ, in the presence of transition metal ions. The H 2 L 2 proligand combines the rigid salen-like coordinating moiety with the flexible Mannich arms, each one with two nitrogen atoms. We have tested its coordination behavior in the reaction with nickel(II) and cobalt(II) as nitrate salts. In both cases, trinuclear complexes of formula [Ni 3 (L 2 )(NO 3 ) 4 ]·CH 3 CN (1) and [Co 3 (L 2 )(NO 3 ) 4 ]·CH 3 CN (2) have been assembled.Two nitrato ligands are chelated to the two peripheral metal ions and the other two act as monoatomic bridges. By reacting these compounds with NaN 3 and NaNCS, the bridging nitrato groups have been replaced by Figure 1. (a) Perspective view of the trinuclear complex 2. (b) Det...

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Section: Resultssupporting

confidence: 88%

Section: Spectral and Magnetic Propertiesmentioning

confidence: 99%

Trinuclear Nickel(II) and Cobalt(II) Complexes Constructed from Mannich–Schiff‐Base Ligands: Synthesis, Crystal Structures, and Magnetic Properties

et al. 2019

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“…It is worth mentioning that these D values are reliable because changing the magnitude or sign of D results in poor fitting of the susceptibility/magnetization data. However, the D values obtained here lie in the range of the reported examples and there are examples of higher D values of Ni II , . It may be mentioned that there is already a report in which different D values of some Ni II compounds were listed …”

Section: Resultssupporting

confidence: 58%

Syntheses, Crystal Structures, and Magnetic Properties of a Series of Defect‐Dicubane Tetranickel(II) Systems with Variable, Mixed, and Interchangeable µ₃‐Core Ligands

2019

Self Cite

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The article describes syntheses, crystal structures and magnetic properties of six defective dicubane type Ni II 4 clusters of compositions [Ni II 4 (HL 1 ) 2 (μ 3 -X) 2 (μ 1,1 -N 3 ) 2 (μ 1,3 -carboxylato) 2 ]· nH 2 O (1, X = OMe -, carboxylato = o-benzoylbenzoato, n = 0; 2, X = {(OMe -) 0.83 (N 3 -) 0.17 }, carboxylato = phenyl acetato, n = 2; 3, (6), where H 2 L 1 is 2-Formyl-6-{(2-hydroxy-1,1-dimethyl-ethylimino)-methyl}-4ethyl-phenol, and this is the partially hydrolyzed product of initially employed ligand H 3 L, 2,6-bis-{(2-hydroxy-1,1-dimethyl- [a] Scheme 2. General schematic illustration of synthetic procedure for all the complexes 1-6.Scheme 3. Schematic representation of solvent-dependent and both-way interconversion between 1 and 4. sorption of strong intensity in the range of 1619-1633 cm -1 , which can be assigned to, respectively, aldehyde C=O and imine C=N stretchings. Symmetric and asymmetric stretchings of μ 1,3carboxylato ligands in 1-5 appear as bands of medium inten-Eur. J. Inorg. Chem. 2019, 4625-4636 www.eurjic.org 4627 sity in the ranges, respectively, 1557-1585 cm -1 and 1380-1409 cm -1 . The O-H stretchings of water (in 2, 5 and 6) or of water and hydroxo (in 4) appear as a broad band with the center lying in the range of 3416-3451 cm -1 . 4634 romagnetic in these three compounds (J 1 = -1.16, -7.33 and -5.59 cm -1 , respectively).

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“…As well known, the magnetic interaction can also be affected by other structural parameters besides the M–O–M angles (γ), such as the dihedral angle (δ) between the MOM plane and the phenyl plane, which also plays a key role in the bis(phenoxo)-bridged M 2 O 2 systems (see Scheme ). ,,, The effect of dihedral angle on magnetic interaction for the Co 2 O 2 system can be explained with the help of magnetic orbitals (Scheme ). The main F contributions are almost not affected by opening the dihedral angle.…”

Section: Resultsmentioning

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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Synthesis, Crystal Structures and Magnetic Properties of Two Heterobridged µ‐Phenoxo‐µ_1,1‐Azide/Isocyanate Dinickel(II) Compounds: Experimental and Theoretical Exploration

Cited by 12 publications

References 96 publications

Trinuclear Nickel(II) and Cobalt(II) Complexes Constructed from Mannich–Schiff‐Base Ligands: Synthesis, Crystal Structures, and Magnetic Properties

Trinuclear Nickel(II) and Cobalt(II) Complexes Constructed from Mannich–Schiff‐Base Ligands: Synthesis, Crystal Structures, and Magnetic Properties

Syntheses, Crystal Structures, and Magnetic Properties of a Series of Defect‐Dicubane Tetranickel(II) Systems with Variable, Mixed, and Interchangeable µ₃‐Core Ligands

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

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Synthesis, Crystal Structures and Magnetic Properties of Two Heterobridged µ‐Phenoxo‐µ1,1‐Azide/Isocyanate Dinickel(II) Compounds: Experimental and Theoretical Exploration

Cited by 12 publications

References 96 publications

Trinuclear Nickel(II) and Cobalt(II) Complexes Constructed from Mannich–Schiff‐Base Ligands: Synthesis, Crystal Structures, and Magnetic Properties

Trinuclear Nickel(II) and Cobalt(II) Complexes Constructed from Mannich–Schiff‐Base Ligands: Synthesis, Crystal Structures, and Magnetic Properties

Syntheses, Crystal Structures, and Magnetic Properties of a Series of Defect‐Dicubane Tetranickel(II) Systems with Variable, Mixed, and Interchangeable µ3‐Core Ligands

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

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Synthesis, Crystal Structures and Magnetic Properties of Two Heterobridged µ‐Phenoxo‐µ_1,1‐Azide/Isocyanate Dinickel(II) Compounds: Experimental and Theoretical Exploration

Syntheses, Crystal Structures, and Magnetic Properties of a Series of Defect‐Dicubane Tetranickel(II) Systems with Variable, Mixed, and Interchangeable µ₃‐Core Ligands