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Issue 41, 2011
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Structural and luminescence studies of nickel(II) and copper(II) complexes with (1R,2R)-cyclohexanediamine derived unsymmetric Schiff base

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Unsymmetrical Schiff base obtained by the condensation reaction of (1R,2R)(−)cyclohexanediamine with 2-hydroxybenzaldehyde and 2-hydroxynaphthaldehyde was used as a ligand for copper(II) and nickel(II). The ligand and complexes were characterized by circular dichroism (CD), UV-VIS, fluorescence, IR and 1H (NOE diff), NOESY and 13C NMR (ligand) spectra. The X-ray crystal structures solved for (1R,2R)(−)chxn(salH)(naftalH) and Cu(II)(1R,2R)(−)chxn(sal)(naftal) revealed tetrahedral distortion of coordination sphere in the solid phase. The [Cu(1R,2R)(−)chxn(sal)(naftal)]·0.5EtOH·1.25H2O complex crystallized in the monoclinic chiral C2 space group with two molecules in the asymmetric unit as well as disordered ethanol and water molecules. For both molecules Cu(II) ions were found in square-planar environments and adopts conformation described as “semi-open armed”, because of distinctly oriented arms according to cyclohexane ring defined by three torsion angles. The thin layers of the ligands, copper(II) and nickel(II) complexes were deposited on Si(111) by a spin coating method and characterized with scanning electron microscopy SEM/EDS and fluorescence spectra. The ligand layers exhibit the most intensive fluorescence band at 498 nm, which can be assigned to emission transition π* → n of Schiff base ligand. For copper(II) layers the most intensive band from intraligand transition at 550 nm was observed. The highest intensity band was registered for the layer obtained when rotation speed was 1000 rpm and time 20 s. The nickel(II) complex layers fluorescence spectra exhibit an intensive band at 564 nm. The emission maxima of the copper(II) and nickel(II) complexes are shifted towards longer wavelength in comparison to the free ligand layers. CD spectra of the complexes in solution are characteristic for tetrahedral planar distortion of the chelate ring. The 1H NMR NOE diff were measured and the position of the nearest hydrogen atoms in the cyclohexane and aromatic rings were discussed, suggesting the tetrahedral distortion of the central ion of the coordination sphere in solution.

Graphical abstract: Structural and luminescence studies of nickel(ii) and copper(ii) complexes with (1R,2R)-cyclohexanediamine derived unsymmetric Schiff base

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The article was received on 10 May 2011, accepted on 04 Aug 2011 and first published on 16 Sep 2011

Article type: Paper
DOI: 10.1039/C1DT10882D
Citation: Dalton Trans., 2011,40, 11012-11022
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    Structural and luminescence studies of nickel(II) and copper(II) complexes with (1R,2R)-cyclohexanediamine derived unsymmetric Schiff base

    M. Barwiolek, E. Szlyk, T. M. Muzioł and T. Lis, Dalton Trans., 2011, 40, 11012
    DOI: 10.1039/C1DT10882D

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