Synthesis, chemical characterization, X-ray crystal structure and magnetic properties of oxalato-bridged copper(II) binuclear complexes with 2,2′-bipyridine and diethylenetriamine as peripheral ligands

Castillo, Óscar; Muga, Iñaki; Luque, Antonio; Gutiérrez‐Zorrilla, Juan M.; Sertucha, Jon; Vitoria, Pablo; Román, Pascual

doi:10.1016/s0277-5387(98)00421-5

Cited by 92 publications

(40 citation statements)

References 48 publications

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“…0.8 Å). All of these are very similar to the structure of [Cu 2 (-ox)(bpy) 2 (H 2 O) 2 -(NO 3 ) 2 ] reported in literature [22] and the only difference is that the coordination environment of two Cu(II) centers is not the same because of the loss of central symmetry resulting from the same arrangement of the methyl groups of chiral pinenobipyridine ligands and the two bond lengths of CuOC(CH 3 ) 2 are not the same (The average bond lengths are 2.784 and 2.440 Å, respectively), while the structure of [Cu 2 (-ox)(bpy) 2 (H 2 O) 2 (NO 3 ) 2 ] with achiral bipyridines is symmetrical.…”

Section: Crystal Structure Of Complexsupporting

confidence: 87%

“…(H 2 O) 2 (ClO 4 ) 2 ] only, which was similar to the way that Castillo et al[22] attempted to synthesize -oxalato heterometal dinuclear Ni/Cu complexes but only dicopper(II) complexes [Cu(-ox)(dien) 2 ](NO 3 ) 2 formed. It was almost the same to the method that Liao et al to provide the bridged oxalates only in the reactions.…”

mentioning

confidence: 53%

“…Julve [20,21], Castillo [22], Tang [23] and Chattopadhyay [24] 4 ] 2+ is coordinated by the two bipyridines and one -oxalato ligands, bond angles of Cu(II) slightly deviate from normal values in the octahedral unit, which could lead to the mixing of d z 2 with d x2y2 magnetic orbitals, and cause a weak ferromagnetic coupling between the orthogonal magnetic orbitals [19]. All of the above demonstrate that the orientation of magnetic orbitals are sensitive to the variety of the coordination environment, which could further affect spin-spin magnetic exchange interaction models between Cu(II) ions.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, characterization, structures and magnetic property of chiral oxalate-bridged dicopper(II) complexes

Wang

Zhu

et al. 2010

Sci. China Chem.

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The oxalato-bridged dicopper(II) complexes [Cu-2(mu-ox)(L-RR)(2)(H2O)(2)(ClO4)(2)] (1), [Cu-2(mu-ox)(L-RR)(2)(CH3COCH3)(2)(ClO4)(2)](1a), [Cu-2(mu-ox)(L-SS)(2)(H2O)(2)(ClO4) 2] (2) and [Cu-2(mu-ox)(L-RR)(L-SS)(2)(CH3COCH3)(2)(ClO4)(2)] (3) [L-RR = (8R, 10R)-(-)-[4,5]-pineno-2,2'- bipyridine, L-SS=(8S, 10S)-(+)-[4,5]-pineno-2,2'-bipyridine; ox(2-) = oxalate] were first prepared. A possible mechanism for the formation of the chial dicopper(II) complexes was proposed. Based on elemental analysis, conductance measurement, UV-Vis spectra, CD spectra and X-ray single-crystal diffraction, the oxalato-bridged structures of 1 and 2 were deduced to adopt two Cu(II) ions and the bridged oxalate lying in the nearly same plane. The crystal structures of 1a and 3 reveal that the coordination geometry around each Cu(II) ion is an elongated and distorted octahedron and two axial solvent molecules and two perchlorate ions are anti to each other respectively in both binuclear molecules. The solution CD spectra of 1 and 2 in the visible d-d range show very weak Cotton effects with peaks at 588 and 779 nm, which are approximately of mirror image, suggesting the optical activities may be derived from the vicinal effects of the chiragenic centers at the pinene group of L-RR and L-SS, respectively. Complex 1 has been characterized by variable-temperature magnetic susceptibility and the data was least-square fitted to the Blenaey-Bowers equation. The exchange integral J was found to be. 338.41(4) cm(-1), indicating a strong antiferromagnetic interaction between two copper(II) ions.National Natural Science Foundation of China [20773098, 20973136]; Innovation Foundation of Xiamen University [XDKJCX20061027

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Section: Crystal Structure Of Complexsupporting

confidence: 87%

mentioning

confidence: 53%

Section: Introductionmentioning

confidence: 99%

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Synthesis, characterization, structures and magnetic property of chiral oxalate-bridged dicopper(II) complexes

Wang

Zhu

et al. 2010

Sci. China Chem.

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“…[1][2][3][4][5]9,10,12,13,15,19,[21][22][23][24][25] Until recently, predictions of the extent of magnetic interactions in dinuclear copper(II) complexes have been largely based upon observations of how certain geometrical features influence magnetism. For example, Hoffmann et al [26] determined that the coupling constant, J, for a d 9 metal complex is given by Equation (2), where |ε S -ε A | 2 is the splitting energy between the singly occupied molecular orbitals and K ab , J aa and J ab are the two-electron integrals involving the localised orthogonal orbitals involved in the magnetic interaction.…”

Section: Magnetostructural Correlationsmentioning

confidence: 99%

“…[4][5][6] Further, theoretical analyses have been undertaken in an effort to develop a molecular orbital view of coupling in these complexes. [7,8] Oxalato-bridged complexes have also been of interest [9][10][11][12][13][14][15] since, in this case, the Cu II centres are linked by multi-atom bridges, yet they can exhibit quite strong anti- [ ferromagnetic interactions even when the Cu II centres are separated by more than 5 Å. [2] Whilst most of these complexes exhibit antiferromagnetic coupling, the strength of this interaction can vary from very weak [2J value (exchange constant) close to 0 cm -1 ] to very strong (2J value up to -400 cm -1 ).…”

Section: Introductionmentioning

confidence: 99%

Oxalato‐Bridged Dinuclear Copper(II) Complexes of N‐Alkylated Derivatives of 1,4,7‐Triazacyclononane: Synthesis, X‐ray Crystal Structures and Magnetic Properties

et al. 2006

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The synthesis, X-ray crystal structure and magnetic properties of two oxalato-bridged dinuclear Cu II complexes, [LCu(µ-ox)Cu-L](ClO 4 ) 2 , where ox = oxalate and L = 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 tacn) or 1-benzyl-4,7-dimethyl-1,4,7-triazacyclononane (BzMe 2 tacn) are reported, as well as the X-ray crystal structure of the mononuclear complex, [Cu(Me 3 tacn)(OH 2 ) 2 ](ClO 4 ) 2 , which features an extended H-bonding network between the ligand and the perchlorate counterions. The crystal structures of the dinuclear complexes both feature a centrosymmetric complex cation in which the two copper centres exist in a distorted squarepyramidal geometry, with each end capped by a facially co-

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Binuclear Nickel(II) Complexes Based on Bridging Oxalate and Pseudohalides as Peripheral Ligands: Synthesis, Crystal Structure, DFT Calculations and Magnetic Properties of [{Ni(X)(dien)}2(μ-ox)]·nH2O Complexes (X = N3−, NCS−,n= 0; NCO−,n= 1)

Muga

Gutiérrez‐Zorrilla

Vitoria

et al. 2000

Eur. J. Inorg. Chem.

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Nickel(II) molecular complexes were obtained by water displacement reactions of [{Ni(dien)(H2O)}2(μ‐ox)]Cl2 and the corresponding pseudohalide. The three nickel(II) compounds [{Ni(N3)(dien)}2(μ‐ox)] (1), [{Ni(NCO)(dien)}2(μ‐ox)] · H2O (2) and [{Ni(NCS)(dien)}2(μ‐ox)] (3) are almost isostructural. The structure determinations reveal the presence of a binuclear complex with C2h symmetry, where the oxalate ligand is coordinated in a bis(bidentate) fashion to the twofold related nickel atoms. The distorted octahedral environment of each nickel atom is completed by the three nitrogen atoms of the diethylenetriamine ligand in a fac arrangement and one nitrogen atom from a pseudohalide ligand. Magnetic susceptibility data in the temperature range 4.2−300 K shows intramolecular antiferromagnetic coupling.

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Synthesis, chemical characterization, X-ray crystal structure and magnetic properties of oxalato-bridged copper(II) binuclear complexes with 2,2′-bipyridine and diethylenetriamine as peripheral ligands

Cited by 92 publications

References 48 publications

Synthesis, characterization, structures and magnetic property of chiral oxalate-bridged dicopper(II) complexes

Synthesis, characterization, structures and magnetic property of chiral oxalate-bridged dicopper(II) complexes

Oxalato‐Bridged Dinuclear Copper(II) Complexes of N‐Alkylated Derivatives of 1,4,7‐Triazacyclononane: Synthesis, X‐ray Crystal Structures and Magnetic Properties

Binuclear Nickel(II) Complexes Based on Bridging Oxalate and Pseudohalides as Peripheral Ligands: Synthesis, Crystal Structure, DFT Calculations and Magnetic Properties of [{Ni(X)(dien)}2(μ-ox)]·nH2O Complexes (X = N3−, NCS−,n= 0; NCO−,n= 1)

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