Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume 2014, Issue 9, Pages 1552-1560Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201301515
Keywords
Copper; Schiff bases; Magnetic properties; Density functional calculations
Categories
Funding
- Balikesir University [BAP-2010/33]
- Scientific and Technological Research Council of Turkey (TUBTAK) [TBAG-108T431]
- Nato-B1-TUBITAK
- Spanish Ministerio de Economia y Competitividad (MINECO) [CTQ-2011-24478/BQU]
- Junta de Andalucia
- University of Granada
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Two alkoxo-bridged copper(II) tridentate Schiff base complexes [{Cu(H(2)L1)}(4)] (1) [H(2)L1 = N-(2-hydroxyethyl)-3,5-di-tert-butylsalicylaldimine] and {Cu(H(2)L2)}(4) (2) [H(2)L2 = N-(2-hydroxyethyl)-4-methoxysalicylaldimine] have been synthesized and structurally and magnetically characterized. X-ray diffraction studies show that 1 and 2 are tetranuclear alkoxo-bridged copper(II) complexes that contain a rather distorted Cu4O4 cubane core of 4+2 type (four short and two long CuCu distances). The coordination of each copper ion can be described as a distorted square pyramid with one nitrogen and four oxygen atoms from three ligands. Variable-temperature magnetic susceptibility measurements on the two tetranuclear complexes 1 and 2 in the range 2-300 K indicate ferromagnetic exchange coupling between copper(II) centers. The magnetic susceptibility data were analyzed by using a simple two-J model with J and J representing the magnetic exchange couplings through the short and long CuCu exchange pathways, respectively. The J values were as follows: J = +28.7 cm(-1) and J = +7.8 cm(-1) for 1, and J = +39.8 cm(-1) and J = +10.2 cm(-1) for 2. The sign and magnitude of the exchange coupling constants were justified on the basis of the structural geometric factors of the bridging Cu(O)(2)Cu fragments, the overlap of the magnetic orbitals, and DFT calculations.
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