Ni^IImolecular complex with a tetradentate aminoguanidine-derived Schiff base ligand: structural, spectroscopic and electrochemical studies and photoelectric response

The new molecular nickel(II) complex, namely, {4-bromo-2-[({N'-[(2-oxidobenzylidene)amino]carbamimidoyl}imino)methyl]phenolato}nickel(II) N,N-dimethylformamide solvate monohydrate, [Ni(C15H11BrN4O2)]·C3H7NO·H2O, (I), crystallizes in the triclinic space group P with one molecule per asymmetric unit. The guanidine ligand is a product of Schiff base condensation between aminoguanidine, salicylaldehyde and 5-bromosalicylaldehyde templated by Ni2+ ions. The chelating ligand molecule is deprotonated at the phenol O atoms and coordinates the metal centre through the two azomethine N and two phenolate O atoms in a cis-NiN2O2 square-planar configuration [average(Ni - N/O) = 1.8489A, cis angles in the range 83.08(5)-95.35(5)°, trans angles of 177.80(5) and 178.29(5)°]. The complex molecule adopts an almost planar conformation. In the crystal, a complicated hydrogen-bonded network is formed through N - H⋯N/O and O - H⋯O intermolecular interactions. Complex (I) was also characterized by FT-IR and 1H NMR spectroscopy. It undergoes an NiII ↔ NiIII redox reaction at E 1/2 = +0.295V (vs Ag/AgCl) in methanol solution. In a thin film with a free surface, complex (I) shows a fast photoelectric response upon exposure to visible light with a maximum photovoltage of ∼178mV.