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Synthesis, Characterization and ESR Studies of New Copper(II) Complexes of Vicinal Oxime Ligands

Mohamad M. E. Shakdofa|Ahmed M. A. El-Seidy|Abdou S. El-Tabl
대한화학회|2011.08|대한화학회지 (Journal of the Korean Chemical Society)|제55권 제4호|pp. 603-611

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참고문헌

키워드

ConductivityMagnetism전기전도도자기적 성질Complexes착물Copper(II)구리(II)OximesESR SpectroscopyESR 분광학
주제분류화학

초록

Ethoxylacetyl oxime ligands [HL, (1) and H_2L^1, (3)] react with copper(II) acetate monohydrate yield octahedral and square planar complexes, respectively. The complexes have been postulated due to elemental analyses, IR, UVVis. spectra, magnetic susceptibility, conductivity and ESR spectra. Molar conductance of the complexes in DMF indicates a non-ionic character. The ESR spectra of [(L)_2Cu(H_2O)_2], (2) complex at room temperature and 77K are characteristic of an axial symmetry (d_(x2-y2)) with covalent bond character and have a large line width typical of dipolar interactions. However, [(L^1)Cu], (4) complex in the solid state showed spectra of marked broadening and loss of hyperfine splitting confirming spinexchange interactions between the copper(II) sites. The spectrum of the doped copper(II) complex at room temperature showed super-hyperfine splitting from coordinated nitrogen atoms and it has an axial type (d_(x2-y2)) with covalent bond character and an essentially square-planar arrangement around the copper(II) ion. The spectrum of [(L^1)Cu], (4) in frozen methanol at 77K was characteristic of the triplet state of a dimer species and the distance found between the two copper(II) centers was calculated and is equal to 4.8 Å.

Abstract

Ethoxylacetyl oxime ligands [HL, (1) and H_2L^1, (3)] react with copper(II) acetate monohydrate yield octahedral and square planar complexes, respectively. The complexes have been postulated due to elemental analyses, IR, UVVis. spectra, magnetic susceptibility, conductivity and ESR spectra. Molar conductance of the complexes in DMF indicates a non-ionic character. The ESR spectra of [(L)_2Cu(H_2O)_2], (2) complex at room temperature and 77K are characteristic of an axial symmetry (d_(x2-y2)) with covalent bond character and have a large line width typical of dipolar interactions. However, [(L^1)Cu], (4) complex in the solid state showed spectra of marked broadening and loss of hyperfine splitting confirming spinexchange interactions between the copper(II) sites. The spectrum of the doped copper(II) complex at room temperature showed super-hyperfine splitting from coordinated nitrogen atoms and it has an axial type (d_(x2-y2)) with covalent bond character and an essentially square-planar arrangement around the copper(II) ion. The spectrum of [(L^1)Cu], (4) in frozen methanol at 77K was characteristic of the triplet state of a dimer species and the distance found between the two copper(II) centers was calculated and is equal to 4.8 Å.

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