EPR Study of 5-Chlorosalicylate-Cu(II)-3-Pyridylmethanol Ternary Complex Systems in Frozen Water–Methanol Solutions

Abstract

Two copper(II) ternary complex systems containing 5-chlorosalicylic acid (5-ClsalH) and different copper(II) salts with varying 3-pyridylmethanol (ron = ronicol) concentration, system I [CuSO₄ (aq) +2(5-ClsalH(solv)) + xron(l)] and system II [Cu(ac)₂(aq) + 2(5-ClsalH(solv)) + xron(l)], where x = 0, 2, 4, 6 and 8, were prepared and studied by electron paramagnetic resonance (EPR) spectroscopy in frozen water–methanol solutions to observe the effects of different copper(II) salts and varying neutral ligand concentration on the formation of resulting complexes in solution. The trend in g-values (g _|| > g _⊥ > 2.0023) indicates that the unpaired electron on the copper ion is localized in the $d_{{x}^{\rm{2}} - {y}^{\rm{2}}}$ orbital. The detailed analysis of the second-derivative Cu(II) EPR spectra has shown well-resolved ¹⁴N superhyperfine splitting in the perpendicular part of the axially symmetric spectra. The resolution of nitrogen superhyperfine multiplet patterns increased with increase in the ronicol concentration (ligand-to-metal ratio x). The number of superhyperfine lines was found to be constant (nonet) when x > 4 for system I and x ≥ 4 for system II. This fact indicates that for these x-values four equivalent nitrogen atoms could be coordinated to the central copper atom in the equatorial plane of both systems.