A hexanuclear copper(II) Schiff base complex incorporating rare “bicapped cubane” core: Structural aspects, magnetic properties and EPR study

Shit, Shyamapada; Nandy, Madhusudan; Rosair, Georgina M.; Fallah, M. Salah El; Ribas, Joan; Garribba, Eugenio; Mitra, Samiran

doi:10.1016/j.poly.2012.07.016

Cited by 19 publications

(8 citation statements)

References 48 publications

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“…9 In recent years, a large number of reports have focused on the synthesis and magnetic properties of chloride-bridged, [10][11][12][13][14][15][16][17][18][19] azide-bridged [20][21][22][23][24][25] or alkoxy-bridged systems. [26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] However, chloride-bridged octahedral-tetrahedral Cu(II) complexes have seldom been reported. [42][43][44] On the other hand, while magneto-structural correlations for azide-Cu(II) systems have been widely investigated, 45,46 those for the chloride-bridged Cu oct -Cl-Cu tet system and dicyanamide-bridged Cu 2 (μ 2 -O) 2 dinuclear systems are not well known.…”

Section: Introductionmentioning

confidence: 99%

Assembly of dinuclear copper(ii) secondary building units into polymeric complexes: crystal structures and magnetic properties

2014

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Four Cu(II) complexes, the one-dimensional [Cu(HL 1 ) 2 (CuCl 4 )] n (1), {[Cu 2 (L 1 ) 2 (N(CN) 2 )(CH 3 OH)](ClO 4 )} n (2), dinuclear [Cu 2 (L 2 ) 2 Cl 2 ] (3), and two-dimensional layered [Cu 2 (L 2 ) 2 (N(CN) 2 ) 2 ] n (4) were synthesized by Cu(II) salts (CuCl 2 •2H 2 O or Cu(ClO 4 ) 2 •6H 2 O), alkanol bidentate ligands trans-2-(1-pyrazolyl)cyclohexanol (HL 1 ) or3,5-dimethyl-N-hydroxyethyl-pyrazolyl (HL 2 ) together with sodium dicyanamide. For complex 1, the bridging chlorine atoms of the tetrahedral [CuCl 4 ] 2− moieties are located at the Jahn-Teller axis of the elongated octahedral Cu(II), forming an alternate elongated-octahedral-tetrahedral Cu(II) chain complex.For complexes 2, 3 and 4, the alkyl oxygen atoms of the deprotonated ligands HL 1 and HL 2 bridge two Cu(II) ions, yielding a dinuclear Cu(II) unit [Cu 2 (L x ) 2 ] 2+ (x = 1, 2), and one-or two-dimensional complexes via bridging dicyanamide ligands. Complex 1 shows weak ferromagnetic coupling, whilst complexes 2-4 display strong antiferromagnetic coupling or are even nearly diamagnetic due to the large Cu-O-Cu bond angles.

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Section: Introductionmentioning

confidence: 99%

Assembly of dinuclear copper(ii) secondary building units into polymeric complexes: crystal structures and magnetic properties

2014

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“…Anal. calcd for C16 H 41 Cu 4 N 8 Ag 1 O 17 : C, 19.61; H, 4.22; N, 11.44. Found: C, 19.71; H, 4.18; N, 11.61%.…”

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confidence: 99%

Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ₄-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

et al. 2013

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The μ4-hydroxo- and alkoxo-bridged tetranuclear copper(II) complexes, [Cu4(μ4-OH)(dmae)4][Ag(NO3)4] (1), [Cu4(μ4-OH)(dmae)4][Na(NO3)4] (2), [Cu4(μ4-OH)(dmae)4][K(NO3)4] (3), and hexanuclear alkoxo-bridged "bicapped cubane" copper(II) complex [Cu6(ae)8(ClO4)2](ClO4)2·MeOH (8) (dmae = N,N-dimethylaminoethanolato and ae = 2-aminoethanolato) were synthesized via self-assembly from chelating amino alcohols and copper(II), silver (1), sodium (2), and potassium (3) nitrates or copper(II) perchlorate (8). The complexes are characterized by elemental analyses, single-crystal X-ray diffraction, and variable temperature magnetic measurements. The crystal structures of complexes 1-3 consist of almost planar tetranuclear [Cu4(μ4-OH)(dmae)4](3+) units, in which Cu(II) ions are also weakly bonded to nitrate anions. The adjacent tetranuclear units of 1-3 are connected by ionic interactions between nitrate anions and sodium, potassium, or silver cations resulting in the formation of 1D polymers. The crystal structure of 8 consists of hexanuclear [Cu6(ae)8](4+) "bicapped cubane" units, in which the capping Cu(II) ions are weakly bonded to perchlorate anions. The adjacent hexanuclear units of 8 are connected by hydrogen bonds resulting in the formation of 3D hydrogen bonded networks. Also the results from the synthetic studies leading to the formation of new copper(II) and silver(I) complexes (4-7) using Hae, 3-aminopropanol (Hap), and N,N-dimethylaminopropanol (Hdmap) in similar reactions, which gave tetra- and hexanuclear complexes, are presented. Experimental magnetic studies showed that complexes 1 and 2 exhibit dominant antiferromagnetic coupling leading to an S = 0 ground state, whereas 8 exhibits a large dominant antiferromagnetic interaction between the capping copper atoms and the copper atoms of the top and bottom faces of the cubane unit that define two isosceles triangles. This interaction leads to an S = 1/2 ground state for each triangle. The weak ferromagnetic interaction between these doublet states through the cubane unit leads to a triplet S = 1 ground state for 8. The values of the magnetic exchange coupling constant were the following: J = +1.8 (1) and +2.9 cm(-1) (2) between adjacent copper atoms; J' = -29.2 (1) and -32.2 cm(-1) (2) between opposite copper atoms; J = -297.6 cm(-1) and zJ' = +0.07 cm(-1) (8). Magnetic coupling constants calculated for 2 and 8 by DFT methods are in general of the same nature and magnitude as the experimental ones.

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“…Many multinuclear transition-metal complexes with various structures have been generated, depending on the disposition of the metal ions and donor sites (N or O). Tetranuclear (Asadi et al, 2018;Manna et al, 2019), pentanuclear (Hari et al, 2019;Ghosh, Cle ´rac et al, 2013) hexanuclear (Shit et al, 2013;Ke ´be ´et al, 2021) and heptanuclear (Gheorghe et al, 2019;Ghosh, Bauza ´et al, 2013) forms have reported with potential applications in the fields of magnetism (Gheorghe et al, 2019), catalysis (Nesterova et al, 2020;Das et al, 2018) or biomimetic synthesis (Nesterova et al, 2020;Sanyal et al, 2017). Our research group has already enabled us to prepare several multidentate Schiff base complexes (Mamour et al, 2018;Sarr et al, 2018a,b;Sall et al, 2019).…”

Section: Chemical Contextmentioning

confidence: 96%

Tetranuclear copper(II) complex of 2-hydroxy-N,N′-bis[1-(2-hydroxyphenyl)ethylidene]propane-1,3-diamine

Diallo¹,

Thiam²,

Gueye-Ndiaye³

et al. 2022

Acta Cryst E

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The title molecular structure, namely, (μ3-acetato)(μ2-acetato)bis(μ3-1,3-bis{[1-(2-oxidophenyl)ethylidene]amino}propan-2-olato)tetracopper(II) monohydrate, [Cu4(C19H19N2O3)2(CH3CO2)2]·H2O, corresponds to a non-symmetric tetranuclear copper complex. The complex exhibits one ligand molecule that connects two copper CuII metal centres via its ethanolato oxygen anion acting in a μ2-mode and one ligand molecule that connects three copper CuII metal centres via its ethanolato oxygen anion acting in a μ3-mode. One bridging acetate group acting in an η1:η1-μ2-mode connects two copper(II) ions while another bridging acetate group connects three copper(II) ions in an η1:-η2-μ3-mode. A chair-like Cu3O3 structure is generated in which the two CuO4N units are connected by one μ2-O ethanolate oxygen atom. These two units are connected respectively to the CuO3N unit via one μ3-O ethanolate oxygen atom and one μ2-O atom from an acetate group. The μ3-O atom also connects one of the CuO4N units and the CuO3N unit to another CuO3N unit, which is out of the chair-like structure. Each of the two pentacoordinated CuII cations has a distorted NO4 square-pyramidal environment. The geometry of each of the two CuNO3 units is best described as a slightly square-planar environment. A series of intramolecular O—H...O hydrogen bonds is observed. In the crystal, the units are connected by intermolecular C—H...O and O—H...O hydrogen bonds, thus forming sheets parallel to the ac plane

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A hexanuclear copper(II) Schiff base complex incorporating rare “bicapped cubane” core: Structural aspects, magnetic properties and EPR study

Cited by 19 publications

References 48 publications

Assembly of dinuclear copper(ii) secondary building units into polymeric complexes: crystal structures and magnetic properties

Assembly of dinuclear copper(ii) secondary building units into polymeric complexes: crystal structures and magnetic properties

Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ₄-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

Tetranuclear copper(II) complex of 2-hydroxy-N,N′-bis[1-(2-hydroxyphenyl)ethylidene]propane-1,3-diamine

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A hexanuclear copper(II) Schiff base complex incorporating rare “bicapped cubane” core: Structural aspects, magnetic properties and EPR study

Cited by 19 publications

References 48 publications

Assembly of dinuclear copper(ii) secondary building units into polymeric complexes: crystal structures and magnetic properties

Assembly of dinuclear copper(ii) secondary building units into polymeric complexes: crystal structures and magnetic properties

Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ4-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

Tetranuclear copper(II) complex of 2-hydroxy-N,N′-bis[1-(2-hydroxyphenyl)ethylidene]propane-1,3-diamine

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Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ₄-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study