Synthesis and Spectroscopic Characterization of Manganese(II), Iron(III) and Cobalt(III) Complexes of Macrocyclic Ligand. Potential of Cobalt(III) Complex in Biological Activity
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A new series of manganese(II), iron(III) and cobalt(III) complexes of 14-membered macrocyclic ligand, (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane-1,8-diamine) have been prepared and characterized by elemental analyses, IR, UVVIS,^1H- and ^13C- NMR spectra, magnetic susceptibilities, conductivities, and ESR measurements. Molar conductance measurements in DMF solution indicate that the complexes are electrolytes. The ESR spectrum for cobalt(III) complex in CD3OD+10%D_2O after exposure to ^(60)Co-γ-rays at 77 K using a 0.2217 M rad h^(-1) vicrad source showed g_⊥>g_(ΙΙ)>g_e, indicating that, the unpaired electron site is mainly present in the d_z2 orbital with covalent bond character. In this case, the ligand hyperfine tensors are nearly collinear with γ-tensors, so there is no major tendency to bend. Therefore, little extra delocalization via the ring lobe of the dz^2 orbital occurs. However, the ESR spectrum in solid state after exposure to ^(60)Co-γ-rays at 77 K showed g_(ΙΙ)>g_⊥>g_e, indicating that, the unpaired electron site is mainly present in the d_x2_(-y)2 ground state as the resulting spectrum contains a large number of randomly oriented molecules provided that, the principle directions of g and A tensors. Manganese (II) complex 2, [H_(12)LMn]Cl_4.2H_2O, showed six isotropic lines characteristic to an unpaired electron interacting with a nucleus of spin 5/2, however, iron(III) complex 3, [H_12LFe]Cl_5.H_2O, showed spectrum of a high spin ^(57)Fe (I=1/2), d^5 configuration. The geometry of these complexes was supported by elemental analyses, IR, electronic and ESR spectral studies. Complex 1 showed exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.
Abstract
A new series of manganese(II), iron(III) and cobalt(III) complexes of 14-membered macrocyclic ligand, (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane-1,8-diamine) have been prepared and characterized by elemental analyses, IR, UVVIS,^1H- and ^13C- NMR spectra, magnetic susceptibilities, conductivities, and ESR measurements. Molar conductance measurements in DMF solution indicate that the complexes are electrolytes. The ESR spectrum for cobalt(III) complex in CD3OD+10%D_2O after exposure to ^(60)Co-γ-rays at 77 K using a 0.2217 M rad h^(-1) vicrad source showed g_⊥>g_(ΙΙ)>g_e, indicating that, the unpaired electron site is mainly present in the d_z2 orbital with covalent bond character. In this case, the ligand hyperfine tensors are nearly collinear with γ-tensors, so there is no major tendency to bend. Therefore, little extra delocalization via the ring lobe of the dz^2 orbital occurs. However, the ESR spectrum in solid state after exposure to ^(60)Co-γ-rays at 77 K showed g_(ΙΙ)>g_⊥>g_e, indicating that, the unpaired electron site is mainly present in the d_x2_(-y)2 ground state as the resulting spectrum contains a large number of randomly oriented molecules provided that, the principle directions of g and A tensors. Manganese (II) complex 2, [H_(12)LMn]Cl_4.2H_2O, showed six isotropic lines characteristic to an unpaired electron interacting with a nucleus of spin 5/2, however, iron(III) complex 3, [H_12LFe]Cl_5.H_2O, showed spectrum of a high spin ^(57)Fe (I=1/2), d^5 configuration. The geometry of these complexes was supported by elemental analyses, IR, electronic and ESR spectral studies. Complex 1 showed exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.
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