Chloro-bridged Cu(II) pairs linked into a 1D coordination polymer through a dinucleating imidazole-based ligand: 3D structure and magnetism

Song, Yu‐Fei; Massera, Chiara; Roubeau, Olivier; Lanfredi, Anna Maria Manotti; Reedijk, Jan

doi:10.1016/j.poly.2005.04.020

Cited by 4 publications

(2 citation statements)

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“…The Cu•••Cu separation is 3.415 Å, not showing interaction between the metal ions. This distance is similar to those found for the chloride dinuclear complexes prepared by Mukherjee et al [29] (3.523 Å) and (4.499 Å) [30]. The DMF solvent molecule was found to be disordered around the twofold axis, in two positions with equal site occupancy (Figure 3b).…”

Section: Crystal Structures Of Complexessupporting

confidence: 86%

Synthesis and characterization of novel M(II) (M = Mn(II), Ni(II), Cu(II) or Zn(II)) complexes with tridentate N2,O-donor ligand (E)-2-amino-N’-[1-(pyridin-2-yl)- ethylidene]benzohydrazide

Kane¹,

Tinguiano²,

Tamboura³

et al. 2016

Bull. Chem. Soc. Eth.

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The coordination chemistry towards the M(II) metal centre (M = Mn, Ni, Cu or Zn) of the hydrazone ligand (E)-2-amino-N'-[1-(pyridin-2-yl)ethylidene]benzohydrazide (H3L) has been explored and complexes having formulae [Mn(H2L)2] (1), {[Ni(H2L)2]. DMF. 0.4H2O} (2), {[Cu2(H2L)2(µ-Cl)2]. DMF} (3) and [Zn(H2L)2] (4) have been isolated and characterized by IR, UV-Visible spectroscopy, elemental analysis and Xray crystal diffraction. Structural studies reveal that the mononuclear complexes (1), (2) and (4) adopt highly distorted octahedral geometries while the dinuclear complex (3) adopts a square pyramidal geometry around each copper(II) ion.

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Section: Crystal Structures Of Complexessupporting

confidence: 86%

Synthesis and characterization of novel M(II) (M = Mn(II), Ni(II), Cu(II) or Zn(II)) complexes with tridentate N2,O-donor ligand (E)-2-amino-N’-[1-(pyridin-2-yl)- ethylidene]benzohydrazide

Kane¹,

Tinguiano²,

Tamboura³

et al. 2016

Bull. Chem. Soc. Eth.

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“…In order to understand the magnetic properties of complicated metallic clusters, scientists must gain fundamental understanding of the magnetic behavior of simpler units. Significant attention has been given to dinuclear systems where the metal centers are directly linked by small anions such as hydroxide, fluoride, chloride, and bromide . With copper(II) in the dihydroxide-bridged systems, it was shown that the magnitude of the antiferromagnetic superexchange interaction, expressed in terms of J (exchange coupling constant) corresponding to the singlet–triplet energy gap, correlates linearly with the Cu–O–Cu angle .…”

Section: Introductionmentioning

confidence: 99%

Dinuclear Metallacycles with Single M–X–M Bridges (X = Cl^–, Br^–; M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)): Strong Antiferromagnetic Superexchange Interactions

et al. 2017

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A series of monochloride-bridged, dinuclear metallacycles of the general formula [M(μ-Cl)(μ-L)](ClO) have been prepared using the third-generation, ditopic bis(pyrazolyl)methane ligands L = m-bis[bis(1-pyrazolyl)methyl]benzene (L), M = Cu(II), Zn(II), and L = m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (L*), M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II). These complexes were synthesized from the direct reactions of M(ClO)·6HO, MCl, and the ligand, L or L*, in the appropriate stoichiometric amounts. Three analogous complexes of the formula [M(μ-Cl)(μ-L)](BF), L = L, M = Cu(II), and L = L*, M = Co(II), Cu(II), were prepared from the reaction of [M(μ-F)(μ-L)](BF) and (CH)SiCl. The bromide-bridged complex [Cu(μ-Br)(μ-L*)](ClO) was prepared by the first method. Three acyclic complexes, [Co(μ-L)μ-Cl], [Co(μ-L*)Cl], and [Co(μ-L*)Br], were also prepared. The structures of all [M(μ-X)(μ-L)] (X = Cl, Br) complexes have two ditopic bis(pyrazolyl)methane ligands bridging two metals in a metallacyclic arrangement. The fifth coordination site of the distorted trigonal bipyramidal metal centers is filled by a bridging halide ligand that has an unusual linear or nearly linear M-X-M angle. The NMR spectra of [Zn(μ-Cl)(μ-L*)](ClO) and especially [Cd(μ-Cl)(μ-L*)](ClO) demonstrate that the metallacycle structure is maintained in solution. Solid state magnetic susceptibility data for the copper(II) compounds show very strong antiferromagnetic exchange interactions, with -J values of 536 cm for [Cu(μ-Cl)(μ-L)](ClO)·xCHCN, 720 cm for [Cu(μ-Cl)(μ-L*)](ClO), and 945 cm for [Cu(μ-Br)(μ-L*)](ClO)·2CHCN. Smaller but still substantial antiferromagnetic interactions are observed with other first row transition metals, with -J values of 98 cm for [Ni(μ-Cl)(μ-L*)](ClO), 55 cm for [Co(μ-Cl)(μ-L*)](ClO), and 34 cm for [Fe(μ-Cl)(μ-L*)](ClO). EPR spectra of [Cu(μ-Cl)(μ-L*)](BF) confirm the d ground state of copper(II). In addition, the sign of the zero-field splitting parameter D was determined to be positive for [Cu(μ-F)(μ-L*)](BF). Electronic spectra of the copper(II) complexes as well as Mössbauer spectra of the iron(II) complexes were also studied in relation with the EPR spectra and magnetic properties, respectively. Density functional theory calculations were performed using ORCA, and exchange integral values were obtained that parallel but are slightly higher than the experimental values by about 30%.

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Tripodal bis(imidazole)-based ligands and their chelation to copper(ii)

et al. 2011

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Three new copper(II) compounds are described containing chelating bis(imidazole)-based ligands. Compound 1, [Cu 2 (L1) 2 (H 2 O) 2 ][SiF 6 ] 2 $10H 2 O, was obtained by reaction of [bis-(1H-imidazol-2-yl)methyl]-pyridin-2-ylmethyl-amine (L1) with Cu(BF 4 ) 2 $6H 2 O in a glass vessel for a few weeks. The single-crystal X-ray structure of 1 consists of dinuclear copper(II) units, formed through ligand sharing. The starting BF 4 À anion was replaced by the SiF 6 2À in the crystal structure of 1. In the crystal lattice, a discrete (H 2 O) 8 cluster forms an eight-membered ring and is linked through four shared water molecules with the other (H 2 O) 8 cluster. Both water clusters show hydrogen-bonding interactions with the neighbouring SiF 6 2À anion. To investigate the effect of the presence of a bridging ligand such as oxalate on the coordination chemistry of L1 and copper(II) ion, compound 2, [Cu 2 (L1)(H 2 O) 2 ][Cu (C 2 O 4 ) 2 (ClO 4 ) 2 ]$2H 2 O, was prepared by reaction of L1 and Cu(ClO 4 ) 2 $6H 2 O in the presence of oxalic acid; the crystal structure is built from 4+ and 4À ions in the crystal lattice. Compound 3, [Cu(ClO 4was formed from the reaction of ligand [bis-(1H-imidazol-2-yl)-methyl]isopropyl-amine (L2) and Cu(ClO 4 ) 2 $6H 2 O in the presence of oxalic acid. The isopropylamine group is not coordinated to the copper in this case, but protonated. In compound 3, a mononuclear copper(II) unit is present, built from a bidentate L2, a bidentate oxalate, a monodentate perchlorate and a water. Two copper coordination entities are doubly bridged through hydrogen bonds with twice the pathway [Cu-O C 2 O 4 -(O water )-Cu] to form a dimeric-like species. Low-temperature magnetic susceptibility studies showed no interaction between copper(II) ions. Scheme 1 A schematic drawing of the molecular structures of [bis-(1Himidazol-2-yl)-methyl]-pyridin-2-ylmethyl-amine (L1) and [bis-(1H-imidazol-2-yl)-methyl]-isopropyl-amine (L2).

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Chloro-bridged Cu(II) pairs linked into a 1D coordination polymer through a dinucleating imidazole-based ligand: 3D structure and magnetism

Cited by 4 publications

References 15 publications

Synthesis and characterization of novel M(II) (M = Mn(II), Ni(II), Cu(II) or Zn(II)) complexes with tridentate N2,O-donor ligand (E)-2-amino-N’-[1-(pyridin-2-yl)- ethylidene]benzohydrazide

Synthesis and characterization of novel M(II) (M = Mn(II), Ni(II), Cu(II) or Zn(II)) complexes with tridentate N2,O-donor ligand (E)-2-amino-N’-[1-(pyridin-2-yl)- ethylidene]benzohydrazide

Dinuclear Metallacycles with Single M–X–M Bridges (X = Cl^–, Br^–; M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)): Strong Antiferromagnetic Superexchange Interactions

Tripodal bis(imidazole)-based ligands and their chelation to copper(ii)

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Chloro-bridged Cu(II) pairs linked into a 1D coordination polymer through a dinucleating imidazole-based ligand: 3D structure and magnetism

Cited by 4 publications

References 15 publications

Synthesis and characterization of novel M(II) (M = Mn(II), Ni(II), Cu(II) or Zn(II)) complexes with tridentate N2,O-donor ligand (E)-2-amino-N’-[1-(pyridin-2-yl)- ethylidene]benzohydrazide

Synthesis and characterization of novel M(II) (M = Mn(II), Ni(II), Cu(II) or Zn(II)) complexes with tridentate N2,O-donor ligand (E)-2-amino-N’-[1-(pyridin-2-yl)- ethylidene]benzohydrazide

Dinuclear Metallacycles with Single M–X–M Bridges (X = Cl–, Br–; M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)): Strong Antiferromagnetic Superexchange Interactions

Tripodal bis(imidazole)-based ligands and their chelation to copper(ii)

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Dinuclear Metallacycles with Single M–X–M Bridges (X = Cl^–, Br^–; M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)): Strong Antiferromagnetic Superexchange Interactions