New complexes of Cu(II) with dipicolinate and pyridyl-based ligands: An experimental and DFT approach

Abstract

The three novel mononuclear copper(II) complexes with dipicolinate and pyridyl-based ligands [Cu(dipic)(L)(OH₂)] (L=4-picoline, vinylpyridine, 4-styrylpyridine; dipic^2-=dipicolinate) were afforded and structurally characterized. X-ray diffraction studies accounted for slight distorted square-pyramidal structures in which the dianion dipic^2- acts as a tridentate ligand in a mer-fashion, the N-donor species occupy an in-plane position, and a water molecule was detected apically coordinated. To assess the effect of the nature of the pyridyl-substituent (para position) on electronic properties, other complexes were also synthesized: [Cu(dipic)(py)(OH₂)], [{Cu(dipic)(OH₂)}₂(μ-pyz)] and [{Cu(dipic)(OH₂)}(μ-pypy){Cu(dipic)}] (py=pyridine, pyz=pyrazine, pypy=(E)-1,2-bis(pyridine-4-yl)ethane). Absorptive behavior in the UV-VIS region was studied in solution and in the solid state (reflectance measurements). Additionally, geometry and population analyses were conducted by means of DFT calculations. Electronic UV-VIS spectra were simulated for both dinuclear complexes in the framework of the TD-DFT methodology to assign the origin of the absorption bands.

Keywords: Coordination chemistry; Cu(II) complexes; DFT; Pyridyl-based ligands; TD-DFT.