Study of the relation between the structural data and magnetic interaction in oxo-bridged binuclear copper(II) compounds

Melnı́k, Milan

doi:10.1016/s0010-8545(00)80537-8

Cited by 401 publications

(123 citation statements)

References 115 publications

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“…Reaction of the parent dinuclear copper(II) carboxylate and linking ligand formed coordination polymers with a one-dimensional chain structure: [Cu2 4 and Cu 2 (catempo) 4 with N,N'-bidentate ligands, L.…”

Section: Synthesis Of Chain Compoundsmentioning

confidence: 99%

“…Copper acetate is one of the old-fashioned metal complexes with a paddle-wheel-like or lantern-like cluster and has attracted much attention since the discovery of the unique dinuclear structure with antiferromagnetic spin-coupling [1][2][3][4][5][6][7]. We have engaged in the synthesis of copper acetate analogues and their coordination polymer complexes [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

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Chain Compounds Based on Paddle-wheel Copper(II) Carboxylate Bearing Four Nitroxide Radicals

et al. 2018

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Chain compounds of paddle-wheel Cu 2 -clusters of 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (Hcaproxy) and 4-carboxy-2,2,6,6-tetramethylpiperidinyloxy (Hcatempo) and N,N'-bidentate ligands (L = 4,4 -bipyridine (4,4 -bpy), 1,2-bis(4-pyridyl)ethane (bpe), trans-1,2-bis(4-pyridyl)ethylene (bpel), 4,4 -dipyridyl disulfide (pds), 1,4-diazabicyclo[2.2.2]octane (dabco), and pyrazine (pyz)), [Cu 2 (caproxy) 4 (L)] n , and [Cu 2 (catempo) 4 (L)] n , were synthesized and characterized by elemental analysis, infrared and UV-vis spectra and temperature dependence of magnetic susceptibilities (4.5-300 K). The crystal structures of [Cu 2 (caproxy) 4 (pds)] n , [Cu 2 (catempo) 4 (4,4 -bpy)] n , and [Cu 2 (catempo) 4 (bpe)] n revealed zigzag or linear chains consisting of alternate arrangement of the dinuclear cluster bearing four nitroxide radicals and N,N'-bidentate ligand. Temperature dependence of magnetic susceptibilities showed a considerable antiferromagnetic interaction between the two copper(II) ions within the dinuclear cluster, and weak antiferromagnetic interaction between the dinuclear clusters and/or the radical and dinuclear cluster.

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Section: Synthesis Of Chain Compoundsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Chain Compounds Based on Paddle-wheel Copper(II) Carboxylate Bearing Four Nitroxide Radicals

et al. 2018

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“…The study of transition metal complexes with four carboxylate bridges (so-called "paddle-wheel") was stimulated by the antiferromagnetic properties of binuclear cupric acetate hydrate due to spin-spin interaction through the bridging carboxylate groups without Cu-Cu bonding (Cu-Cu 2.64 Å) [2,3]. The analogous carboxylate complexes of other 3d-metals were prepared lately with using of steric effects of axial ligands: alphasubstituted pyridines (2-picoline, 2,6-lutidine, acridine or N,Ndimethylformamide) or cyclopentadienyl groups [4][5][6][7].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of tetra(3-carboxyl-2,2,5,5-tetramethylpyrrolidin-1-oxyl) bis(dimethyl fumarate) bicopper(II) complex, C21H37CuN3O7

Niu

Zheng²,

et al. 2013

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of material 4-oxo-2,2,6,6-tetramethylpiperdin-1-oxyl I can be conveniently obtained by procedures given in the literature [1].The reaction of I with concentrated hydrochloric acid gave the isolable intermediate l-hydroxy-4-oxo-2,2,6,6-tetramethylpiperidine hydrochloride II which then was brominated to the 3-bromo-l-hydroxy-4-oxo-2,2,6,6-tetramethylpiperidine derivative which, in turn, was converted in situ to the corresponding radical III by oxidation using sodium nitrite. Compound III (25 g, 0.1 mmol) was added, portionwise, to a stirred solution of sodium hydroxide (8 g, 0.2mol) in water (150 mL). The reaction mixture was stirred for 3 h at about 20°C, acidified with 6 mol/L aqueous HC1 solution to pH 2, and quickly extracted with chloroform (3´80 mL). The organic layer was dried with anhydrous magnesium sulfate. After removal of the solvent in a rotating evaporator, the residue was recrystallized from a mixture of chloroform and hexane (3/1, v/v) to give 14.8 g (79.5%) of the yellow product IV.A solution of HCTemPO (372 mg, 2 mmol) in water (10 mL) was dropped slowly into CuO (80 mg, 1 mmol) in water (5 mL). DiscussionThe study of transition metal complexes with four carboxylate bridges (so-called "paddle-wheel") was stimulated by the antiferromagnetic properties of binuclear cupric acetate hydrate due to spin-spin interaction through the bridging carboxylate groups without Cu-Cu bonding (Cu-Cu 2.64 Å) [2,3]. The analogous carboxylate complexes of other 3d-metals were prepared lately with using of steric effects of axial ligands: alphasubstituted pyridines (2-picoline, 2,6-lutidine, acridine or N,Ndimethylformamide) or cyclopentadienyl groups [4][5][6][7]. [7]. The coordination of each Cu(II) ion is a distorted tetragonal pyramid. The Addison's criterion, which is 1 for an ideal trigonal bipyramid and 0 for an ideal tetragonal pyramid, respectively [9], has a value of 0.016 for the title moiety. The longer (Cu1-O7 DMF = 2.125(2) Å) distance is viewed at the apical position. The Cu1 atom deviates by 0.2049 Å from the basal plane formed by the O1, O2, O3 and O4 atoms. A DMF molecule is bound trans to the Cu1-Cu1A vector on each of the Cu atoms, and a further two DMF molecules are loosely held in the lattice. These lattice DMF sites were highly mobile, and their sites were only partially occupied. During the data collection, some reductions in the intensities of the standard reflections were noted, and these are consistent with slow loss of these molecules of crystallization. The fused and conjugated five-membered rings are close to being planar (deviations less than 0.2339 Å), and the molecule makes no close contacts with other molecules in the structure. The two copper atoms in each dimeric unit are separated by a distance of

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“…Intramolecular magnetic exchange coupling in dinuclear copper(II) compounds was first recognized in copper(II) acetate hydrate, in which two Cu(II) ions are bridged symmetrically by four acetate groups [1]. Since then a variety of tetrakis(m-carboxylato) complexes [Cu 2 (O 2 CR) 4 X 2 ] with strong intramolecular antiferromagnetism has been reported [2,3]. The title crystal structure consists of dimeric units.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of bis(μ2-malato)-bis(pyrazino(2,3-f)quinoxaline)- dicopper(II), Cu2(C4H4O5)2(C10H6N4)2

Li¹,

Li²,

Fu³

et al. 2007

Zeitschrift Für Kristallographie - New Crystal Structures

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C 28 H 20 Cu 2 N 8 O 10 , monoclinic, P12 1 /n1 (no. 14), a = 11.887(2) Å, b = 9.422(2) Å, c = 13.535(2) Å, b = 108.74(1)°, V = 1435.5 Å 3 , Z = 2, R gt (F) = 0.055, wR ref(F 2 ) = 0.104, T = 296 K. Source of materialThe title compound was synthesized with the hydrothermal method from a mixture of malic acid (1 mmol), copper(II) acetate monohydrate (0.5 mmol), pyrazino(2,3-f )quinoxaline (1 mmol, pzq), 0.05 ml Et 3N and 8 ml deionized water (20 ml) in a 25 ml Teflon-lined stainless steel reactor. The solution was heated to 424 K for three days. After the reaction system was slowly cooled to room temperature, then the blue prism-shaped crystals were collected and washed with distilled water. Experimental detailsThe C12, C13 and O3 atoms are disordered. The atoms were refined isotropically and under using of bond restraints, the refined occupancy factors are approximately 0.50 each (ratio = 0.49(1)/ 0.51). While the H atoms associated with C atoms were added geometrically, the positions of the H atoms bound to O atoms were refined. The two Cu(II) centers are bridged by two O atoms of carboxylate groups in the less-common monoatomic bridging mode, with a C11O1 distance of 1.279(7) Å being significantly longer than the C11O2 distance of 1.209(7) Å as expected for this type of bond. The separation between the two copper atoms and CuOCu bridging angles in the dimer are 3.497 Å and 104.8°, respectively. Through aromatic p-p stacking interactions between the pzq (face-to-face distance of 3.747 Å), adjacent dinuclear Cu(II) units are linked into one-dimensional chain along the a axis. Moreover, the intermolecular CH···O bond (3.165 Å 3.411 Å) and OH···O bond (2.646 Å) further connect neighboring chains into a 3D supramolecular architecture. Discussion

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Study of the relation between the structural data and magnetic interaction in oxo-bridged binuclear copper(II) compounds

Cited by 401 publications

References 115 publications

Chain Compounds Based on Paddle-wheel Copper(II) Carboxylate Bearing Four Nitroxide Radicals

Chain Compounds Based on Paddle-wheel Copper(II) Carboxylate Bearing Four Nitroxide Radicals

Crystal structure of tetra(3-carboxyl-2,2,5,5-tetramethylpyrrolidin-1-oxyl) bis(dimethyl fumarate) bicopper(II) complex, C21H37CuN3O7

Crystal structure of bis(μ2-malato)-bis(pyrazino(2,3-f)quinoxaline)- dicopper(II), Cu2(C4H4O5)2(C10H6N4)2

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