Dinuclear copper(II) complexes of a novel 3-(aminomethyl)naphthoquinone Mannich base: Synthesis, structural, magnetic and electrochemical studies

A novel versatile tridentate 3-(aminomethyl)naphthoquinone proligand, 3-[N-(2-pyridylmethyl)aminobenzyl]-2-hydroxy-1,4-naphthoquinone (HL), was obtained from the Mannich reaction of 2-hydroxy-1,4-naphthoquinone (Lawsone) with 2-aminomethylpyridine (amp) and benzaldehyde. The reactions of HL with CuCl2·2H2O yielded two novel dinuclear copper(II) complexes, [Cu(L)(H2O)(μ-Cl)Cu(L)Cl] (1b), [CuCl(L)(μ-Cl)Cu(amp)Cl] (2) and a polymeric compound, [Cu(L)Cl)]n (1a), whose relative yields were sensitive to temperature, reagents concentration and presence of base. The crystalline structures of 1b and 2 were determined by X-ray diffraction studies. The two copper atoms in complex 1b are connected by a single chloro bridge with a Cu⋯Cu separation of 4.1342(8) Å and Cu(1)–Cl(1)–Cu(2) angle of 109.31(4)°. In complex 2 the two copper atoms are held together by a chloro and a naphthalen-2-olate bridges [Cu(1)–Cl(2)–Cu(2) and Cu(1)–O(1)–Cu(2) angles being 83.31(3) and 109.70(9)°, respectively, and the Cu⋯Cu separation, 3.3476(9) Å]. As expected, variable-temperature magnetic susceptibility measurements of complex 1b showed weak antiferromagnetic intramolecular coupling between the copper(II) centers, with J = −5.7 cm−1, and evidenced for complex 2 strong antiferromagnetic coupling, with J ∼ −120 cm−1. Furthermore, the magnetic behaviour of compound 1a suggested an infinite 1D coordination polymeric structure in which the copper(II) centers are connected by Cl–Cu–Cl bridges. Solution data (UV–Vis spectroscopy and cyclic voltammetry) indicated structural changes of 2 and 1a in CH3CN, and evidenced conversion of polymer 1a into dimer 1b.

Graphical abstractThe reactions of novel 3-[N-(2-pyridylmethyl)aminobenzyl]-2-hydroxy-1,4-naphthoquinone (HL) with CuCl2·2H2O yielded two dinuclear copper(II) complexes, [Cu(L)(H2O)(μ-Cl)Cu(L)Cl] (1b) and [CuCl(L)(μ-Cl)Cu(amp)Cl] (2) with unprecedented structures. Electrochemical and magnetic studies are also reported.Figure optionsDownload full-size imageDownload as PowerPoint slide