Synthesis, crystal structure, EPR and electrochemical studies of copper(II) dipicolinate complex with 2,2′-dipyridylamine ligand

Abstract

The (2,2′-dipyridylamine)(pyridine-2,6-dicarboxylato)copper(II) trihydrate complex was synthesized and characterized by spectroscopic (IR, UV–vis, EPR), X-ray diffraction technique and electrochemical methods. The copper(II) center is surrounded by one bidentate 2,2′-dipyridylamine (dpa) and one tridentate dipicolinate (dpc) ligand, and exhibits a distorted square-pyramidal geometry. The crystal packing involves both hydrogen-bonding and π– π interactions. The solvent water molecules link monomers to one another through hydrogen-bonding interactions, forming ladder-type chains in the ab plane. π– π interactions also occur between the dpa rings of neighboring molecules and are responsible for interchain packing. Based on EPR and optical absorption studies, spin-Hamiltonian and bonding parameters have been calculated. The g-values, calculated for title complex in polycrystalline state at 298 K and in frozen DMF (110 K), indicate the presence of the unpaired electron in the d x 2 - y 2 orbital. The evaluated metal–ligand bonding parameters showed strong in-plane σ- and π-bonding. The cyclic voltammogram of the title complex investigated in DMF (dimethylformamide) solution exhibits only metal centered electroactivity in the potential range ±1.25 V versus Ag/AgCl reference electrode.