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

作者：Luzardo Florencia; Alvarez Natalia; Kremer Carlos; de Camargo Andrea S S; Gancheff Jorge S^*

来源：Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy , 2017, 183: 45-52.

DOI：10.1016/j.saa.2017.04.003

• Coordination chemistry
• Cu(II) complexes
• Pyridyl-based ligands
• DFT
• TD-DFT

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: ICu(diPic)(PY)(OH2)], [{Cu(dipic)(OH2))(2)(mu-PYz)] and [{Cu(diPic)(OH2)}(mu-PYPY)(Cu(diPic)}] (py = pyridine, pyz = pyrazine, pypy = (E)-1,2-bis(pyridine-4-yl)ethane). Absorptive behavior in the IJV-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.

• 出版日期2017-8-5