Synthesis,structures, and property studies on Zn(II), Ni(II), and Cu(II) complexes with a Schiff base ligand containing thiocarbamide group |
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Authors: | Pu Su Zhao Hong Yan Wang Jie Song Lu De Lu |
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Institution: | (1) Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, Huaiyin Normal University, Huaian, Jiangsu, 223300, People’s Republic of China;(2) Materials Chemistry Laboratory, Nanjing University of Science and Technology, Nanjing, Jiangsu, 210094, People’s Republic of China; |
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Abstract: | A Schiff base ligand containing thiocarbamide group of 4-phenyl-1-(4-methoxyl-1-phenylethylidene)thiosemicarbazide (HL) and
its three mononuclear metal complexes of ZnL2 (1), NiL2 (2), and CuL2 (3) have been synthesized. Elemental analysis, IR, and X-ray single crystal diffraction characterizations for the ligand and
the three complexes have been carried out. In the three complexes, the central metallic ions of Zn2+, Ni2+, and Cu2+ coordinate with two deprotonated ligands of L−, respectively. In 1, Zn2+ ion adopts a distorted tetrahedral geometry, while in 2 and 3, both the Ni2+ and Cu2+ ions possess distorted square planar configurations. For the four compounds, UV–Vis spectra have been measured and DFT calculations
at B3LYP/LANL2DZ level of theory prove that the electronic spectra of HL and 1 are corresponding with electronic transitions of n → π* and π → π* in the ligand itself and the electronic spectra of 2 and 3 are attributed to intraligand electronic transitions as well as d–d electronic transitions. Electrochemical investigations reveal that the different metal–ligand interactions have changed the
peak shapes and peak locations, which are corresponding with the DFT-B3LYP/LANL2DZ calculational results. Fluorescence spectra
measurements indicate that the ligand emits purple fluorescence and the complex 1 emits stronger blue fluorescence, while the complexes 2 and 3 quench fluorescence. The thermal analyses result show that the three complexes undergo two similar decomposition processes
because of their similar geometric configurations. |
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