Metal complexes of a pentadentate N2O3bis(semicarbazone) Schiff-base. A case study of structure-spectroscopy correlation

• Electronic transitions and EPR tensors pointed to molecular distortions in dinuclear complexes
• Electronic and molecular structure of a multifucional bis(semicarbanoze) ligand
• ZINDO/S and MM+ semiempirical calculations support the spectral assignment

Schiff condensation of 2,6-diformyl 4-methylphenol with semicarbazide hydrochloride in 1:2 molar ratio produces the bis(semicarbazone) ligand, herein called H3L. A comprehensive spectroscopic analysis of the compound was performed by 1H and 13C NMR, FTIR and electronic spectroscopies. Assignments to the UV–vis spectrum of H3L were supported by semi-empirical quantum mechanics ZINDO/S calculations. The ligand H3L forms monoclinic crystals in the space group P21/c and its structure is stabilized by classic hydrogen bonds with propanone molecules. It promptly reacts with first row metal ions to produce the following coordination compounds: [Co2(L)(μ-NO3)]·DMF, [Ni2(H2L)(μ-CH3COO)(CH3COO)2]·2H2O, [Cu2(L)(μ-NO3)(H2O)2]·H2O, [Cu2(L)(μ-CH3COO)(H2O)2]·H2O and [Cu2(H2L)(μ-Cl)Cl2]·3H2O, that have different compositions, depending on the degree of deprotonation of the ligand upon coordination. Electronic and EPR spectroscopies as well as effective magnetic moment measurements of the complexes were used in an attempt to better understand their mode of coordination, the microsymmetry around the metal ions and magnetic properties.

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