Bis[N-2-(R-pyridyl)-2-oxo-1-naphthaldiminato-κ2NO]copper(II) (R = H, 4/6-CH3): Combined studies on syntheses, spectroscopy, cyclic voltammetry, thermal analyses, crystal structure and DFT/TDDFT

Reaction of pyridyl Schiff base ligands, N-2-(R-pyridyl)-2-hydroxy-1-naphthaldimine (HL) with copper (II) acetate provides the bis[N-2-(R-pyridyl)-2-oxo-1-naphthaldiminato-kappa N-2<^>O]copper(II) (R = H: 1, 4/6-CH3: 2/3). Electronic spectra show the bands at <350, 350-500, and 500-850 nm for intra-ligand, metal-ligand, metal-metal transitions, respectively in dichloromethane. Thermal analyses demonstrate an irreversible phase transformation from crystalline to crystal-liquid, and to isotropic liquid phase. Cyclic voltammogram exhibits a quasi-reversible two electrons transfer for [Cu(L)(2)]/[Cu(L)(2)](-) and [Cu (L)(2)]-/[Cu(L)(2)](2-) couples, respectively in acetonitrile. Magnetic moment values (mu = 1.35 (1), 1.40 (2), and 1.42 (3) mu B at 23 degrees C} indicate the formation of copper(II)-N<^>O chelate complexes with one unpaired electron in dichloromethane. X-ray structure determination for 3 verifies its roughly square-planar coordination by two N<^>O-chelating ligands to the copper(II). Optimized geometry by DFT corresponds well to the experimental structures. Electronic spectra by TDDFT explore a combined metal-metal, metal-ligand, and ligand-ligand transitions band with the highest MO contributions of 98% at ca. 388 nm (HOMO-1 to LUM0+1 for 1) or 99% at ca. 413 nm (HOMO to LUMO for 3), very close to the experimental results. (C) 2016 Elsevier B.V. All rights reserved.