A ferromagnetically coupled single hydroxido bridged tetranuclear nickel(II) Schiff base complex incorporating a Ni4O4 cubane core: Crystal structure and magnetic study

Shit, Shyamapada; Nandy, Madhusudan; Rosair, Georgina M.; Gómez‐García, Carlos J.; Almenar, Juan J Borras; Mitra, Samiran

doi:10.1016/j.poly.2013.05.029

Cited by 26 publications

(5 citation statements)

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“…However, the dihedral Ni-O-O-Ni angle also plays an important role. 28 In compound 1 these dihedral angles are far from 180°(these are 139.35°for Ni1-O11-O31-Ni2 and 157.38°for Ni2-O41-O61-Ni3) and, therefore, the magnetic coupling is expected to be weak and antiferromagnetic, as observed experimentally. In compound 2 the weak antiferromagnetic coupling found ( J = −2.4 cm −1 ) is not surprising since the two Ni(II) ions are bridged by a double asymmetric phenoxido bridge.…”

Section: Magnetic Propertiesmentioning

confidence: 85%

Influence of the central metal ion in controlling the self-assembly and magnetic properties of 2D coordination polymers derived from [(NiL)₂M]²⁺ nodes (M = Ni, Zn and Cd) (H₂L = salen-type di-Schiff base) and dicyanamide spacers

2015

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Three new 2D coordination polymers (CPs) (2)∞[(NiL)2Ni(μ1,5-N(CN)2)2]n (), (2)∞[(NiL)2Cd(μ1,5-N(CN)2)2]n () and (2)∞[(NiL)2Zn(μ1,5-N(CN)2)2]n () have been synthesized by reacting a [NiL] "metalloligand" (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) with three different metal(ii) (Ni, Cd and Zn) perchlorates and sodium dicyanamide, with identical molar ratios of the reactants. All three products have been characterized by IR and UV-Vis spectroscopies, elemental analyses, powder and single crystal X-ray diffraction and variable temperature magnetic measurements. The isomorphous compounds and consist of similar [(NiL)2M(μ1,5-N(CN)2)] (M = Ni for and Cd for ) angular trinuclear units in which two terminal "metalloligands" [NiL] coordinate to the central nickel(ii) (in ) or cadmium(ii) (in ) ion through phenoxido oxygen atoms. The μ1,5-bridging dicyanamido spacers connect the central Ni(ii) or Cd(ii) of one node to terminal Ni(ii) of two different nodes giving rise to 2D CPs. Compound also contains trinuclear units with the same formula as those of and : [(NiL)2M(μ1,5-N(CN)2)] (M = Zn in ). The main differences are that these units are linear in and the dicyanamide spacers link only the nickel atoms of neighbouring nodes. As in and , these trinuclear units are connected to four other units via four μ1,5-bridging dicyanamido ligands, giving rise to 2D CP with a similar topology: a uninodal 4-connected underlying net with the sql (Shubnikov tetragonal plane net) topology and (4(4)·6(2)) point symbol. The magnetic properties show the presence of moderate intra-trimer antiferromagnetic interactions in (J = -12.9 cm(-1)) and weak antiferromagnetic interactions between the terminal Ni(ii) ions in (J = -2.4 cm(-1)). In the Ni(ii) ions are well isolated by the central Zn(ii) ion and accordingly, only a very weak antiferromagnetic interaction through the single μ1,5-bridging dicyanamido ligands is observed (J = -0.44 cm(-1), D = -3.9 cm(-1)).

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Section: Magnetic Propertiesmentioning

confidence: 85%

Influence of the central metal ion in controlling the self-assembly and magnetic properties of 2D coordination polymers derived from [(NiL)₂M]²⁺ nodes (M = Ni, Zn and Cd) (H₂L = salen-type di-Schiff base) and dicyanamide spacers

2015

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“…Many polynuclear complexes of transition metals with various structures can be generated, depending on the disposition of the metal ions and the donor sites (N or O). Trimers (Zhang et al, 2009), square shapes (Aouaidjia et al, 2017), cyclic forms (Acevedo-Chá vez et al, 2002) and cubans (Shit et al, 2013) have been reported that have potential applications in the field of magnetism (Shit et al, 2013), catalysis (Okeke et al, 2018) and biomimetic synthesis (Wu et al, 2004). By extension, the introduction of an ethoxy-carbonyl group in the ortho position of the pyridine gives a ligand that can have a similar behavior to -amino acid esters.…”

Section: Chemical Contextmentioning

confidence: 99%

Crystal structures of two Cu^II compounds: catena-poly[[chloridocopper(II)]-μ-N-[ethoxy(pyridin-2-yl)methylidene]-N′-[oxido(pyridin-3-yl)methylidene]hydrazine-κ⁴ N,N′,O:N′′] and di-μ-chlorido-1:4κ² Cl:Cl-2:3κ² Cl:Cl-dichlorido-2κCl,4κCl-bis[μ₃-ethoxy(pyridin-2-yl)methanolato-1:2:3κ³

Sall

Tamboura

et al. 2019

Acta Cryst E

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Two CuII complexes [Cu(C14H13N4O2)Cl] n , I, and [Cu4(C8H10NO2)4Cl4] n , II, have been synthesized. In the structure of the mononuclear complex I, each ligand is coordinated to two metal centers. The basal plane around the CuII cation is formed by one chloride anion, one oxygen atom, one imino and one pyridine nitrogen atom. The apical position of the distorted square-pyramidal geometry is occupied by a pyridine nitrogen atom from a neighbouring unit, leading to infinite one-dimensional polymeric chains along the b-axis direction. Each chain is connected to adjacent chains by intermolecular C—H...O and C—H...Cl interactions, leading to a three-dimensional network structure. The tetranuclear complex II lies about a crystallographic inversion centre and has one core in which two CuII metal centers are mutually interconnected via two enolato oxygen atoms while the other two CuII cations are linked by a chloride anion and an enolato oxygen. An open-cube structure is generated in which the two open-cube units, with seven vertices each, share a side composed of two CuII ions bridged by two enolato oxygen atoms acting in a μ3-mode. The CuII atoms in each of the two CuO3NCl units are connected by one μ2-O and two μ3-O atoms from deprotonated hydroxyl groups and one chloride anion to the three other CuII centres. Each of the pentacoordinated CuII cations has a distorted NO3Cl square-pyramidal environment. The CuII atoms in each of the two CuO2NCl2 units are connected by μ2-O and μ3-O atoms from deprotonated alcohol hydroxy groups and one chloride anion to two other CuII ions. Each of the pentacoordinated CuII cations has a distorted NO2Cl2 square-pyramidal environment. In the crystal, a series of intramolecular C—H...O and C—H...Cl hydrogen bonds are observed in each tetranuclear monomeric unit, which is connected to four tetranuclear monomeric units by intermolecular C—H...O hydrogen bonds, thus forming a planar two-dimensional structure in the (\overline{1}01) plane.

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“…In recent years, some progress has been made in magnetic research of metal–oxo clusters based on an M 4 O 4 cubane core. − We found that cubic alkoxide clusters based on different magnetic metals (Fe, Cu, Ni, Co, Mn, etc.) may have different magnetic interactions.…”

Section: Introductionmentioning

confidence: 99%

Design and Self-Assembly of Ferrocene-Functional Heterometal–Oxo Clusters with the M(III)₄O₄ Cubane Core

Lan,

Wang,

Lin

et al. 2024

Crystal Growth & Design

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In this work, we synthesized two Cu-based heterometal−oxo clusters 1 and 2 based on M(III) 4 O 4 (M = Fe/ In) cubane centers and obtained the corresponding dimers 3 and 4 by connecting Cu atoms on the cluster cores with the auxiliary ligand 4,4′-bipyridine. They were characterized by single-crystal Xray diffraction (SCXRD), powder X-ray diffraction (PXRD), and other tests. We conducted magnetic property study on compounds 1−4. The variable-temperature magnetic susceptibility test shows that compounds 1 and 3 exhibit significant ferromagnetic interactions at low temperatures, while compounds 2 and 4 exhibit overall antiferromagnetic interactions. When the metal at the cubane changes from magnetic Fe to nonmagnetic In, the magnetic interactions in the compound are weakened to a certain extent. Through dimerization, the extreme values of the variable-temperature magnetic susceptibility appear (1 to 3)/disappear (2 to 4) in the low-temperature section. We investigated the magnetic structure correlation of compounds 1−4 through bond lengths, bond angles, and distances between magnetic atoms. The results showed that compounds 1−4 exhibited significant magnetic coupling diversity.

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A ferromagnetically coupled single hydroxido bridged tetranuclear nickel(II) Schiff base complex incorporating a Ni4O4 cubane core: Crystal structure and magnetic study

Cited by 26 publications

References 58 publications

Influence of the central metal ion in controlling the self-assembly and magnetic properties of 2D coordination polymers derived from [(NiL)₂M]²⁺ nodes (M = Ni, Zn and Cd) (H₂L = salen-type di-Schiff base) and dicyanamide spacers

Influence of the central metal ion in controlling the self-assembly and magnetic properties of 2D coordination polymers derived from [(NiL)₂M]²⁺ nodes (M = Ni, Zn and Cd) (H₂L = salen-type di-Schiff base) and dicyanamide spacers

Design and Self-Assembly of Ferrocene-Functional Heterometal–Oxo Clusters with the M(III)₄O₄ Cubane Core

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A ferromagnetically coupled single hydroxido bridged tetranuclear nickel(II) Schiff base complex incorporating a Ni4O4 cubane core: Crystal structure and magnetic study

Cited by 26 publications

References 58 publications

Influence of the central metal ion in controlling the self-assembly and magnetic properties of 2D coordination polymers derived from [(NiL)2M]2+ nodes (M = Ni, Zn and Cd) (H2L = salen-type di-Schiff base) and dicyanamide spacers

Influence of the central metal ion in controlling the self-assembly and magnetic properties of 2D coordination polymers derived from [(NiL)2M]2+ nodes (M = Ni, Zn and Cd) (H2L = salen-type di-Schiff base) and dicyanamide spacers

Crystal structures of two CuII compounds: catena-poly[[chloridocopper(II)]-μ-N-[ethoxy(pyridin-2-yl)methylidene]-N′-[oxido(pyridin-3-yl)methylidene]hydrazine-κ4 N,N′,O:N′′] and di-μ-chlorido-1:4κ2 Cl:Cl-2:3κ2 Cl:Cl-dichlorido-2κCl,4κCl-bis[μ3-ethoxy(pyridin-2-yl)methanolato-1:2:3κ3

Design and Self-Assembly of Ferrocene-Functional Heterometal–Oxo Clusters with the M(III)4O4 Cubane Core

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Influence of the central metal ion in controlling the self-assembly and magnetic properties of 2D coordination polymers derived from [(NiL)₂M]²⁺ nodes (M = Ni, Zn and Cd) (H₂L = salen-type di-Schiff base) and dicyanamide spacers

Influence of the central metal ion in controlling the self-assembly and magnetic properties of 2D coordination polymers derived from [(NiL)₂M]²⁺ nodes (M = Ni, Zn and Cd) (H₂L = salen-type di-Schiff base) and dicyanamide spacers

Design and Self-Assembly of Ferrocene-Functional Heterometal–Oxo Clusters with the M(III)₄O₄ Cubane Core