Tetranuclear Copper(II) Complexes Bearing Cu4O6 and Cu4O4 Cores: Synthesis, Structure, Magnetic Properties, and DFT Study

被引:17
作者
Banerjee, Atanu [1 ]
Singh, Reena [1 ]
Mondal, Pallab [1 ]
Colacio, Enrique [2 ]
Rajak, Kajal Krishna [1 ]
机构
[1] Jadavpur Univ, Dept Chem, Inorgan Chem Sect, Kolkata 700032, India
[2] Univ Granada, Fac Ciencias, Dept Quim Inorgan, E-18071 Granada, Spain
关键词
Tetranuclear complexes; Magnetic properties; Density functional calculations; Copper; DENSITY-FUNCTIONAL CALCULATIONS; TRANSITION-METAL-COMPLEXES; NEUTRON-SCATTERING SPECTRA; VALENCE-BOND THEORY; CRYSTAL-STRUCTURES; MAGNETOSTRUCTURAL CORRELATIONS; ELECTRONIC-STRUCTURE; EXCHANGE INTERACTIONS; CHEMICAL-PARAMETERS; BINUCLEAR COMPLEXES;
D O I
10.1002/ejic.200900709
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of Cu(ClO4)(2)center dot 6H(2)O with N4O3 coordinating heptadentate (H3L1) and N2O coordinating tridentate reduced Schiff base (HL2) ligands yielded copper(II) tetra-nuclear complexes [Cu-4(L-1)(2)](ClO4)(2) (1) and [Cu-4(L-2)(4)](ClO4)(4) (2), respectively. Complex 1 crystallizes in the cubic system, space group Fd (3) over barc, with unit-cell parameters a = b = c = 43.124(5) angstrom, Z = 48, whereas complex 2 crystallizes in the space group P4(1)2(1)2 in the tetragonal crystal system with Z = 8 and unit-cell parameters a = b = 17.1.13(4) angstrom, c = 44.150(4) angstrom. The X-ray structures of 1 and 2 have revealed a Cu4O6 core in I and a Cu4O4 core in 2. Complexes 1 and 2 show intramolecular antiferromagnetic interaction with moderate vertical bar J vertical bar values (104.2 cm(-1) for 1 and 155.1 cm(-1) for 2). The moderate vertical bar J vertical bar value can be explained by the existence of only one bridging alkoxido group between each pair of copper(II) atoms and the out-of-plane displacement of the alkoxido carbon atom from the Cu-O-Cu plane, Broken-symmetry density functional theory (BSDFT) has been used to justify the exchange pathways.
引用
收藏
页码:790 / 798
页数:9
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