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Synthesis, structure, spectroscopic properties, electrochemistry, and DFT correlative studies of N-[(2-pyridyl)methyliden]-6-coumarin complexes of Cu(I) and Ag(I) |
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| Authors: | Suman RoyTapan Kumar Mondal Partha MitraElena Lopez Torres Chittaranjan Sinha |
| Institution: | a Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata 700 032, India b Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India c Departamento de Química Inorgánica, c/ Francisco Tomás y Valiente, 7, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid, Spain |
| Abstract: | 6-Aminocoumarin reacts with pyridine-2-carboxaldehyde and has synthesized N-(2-pyridyl)methyliden]-6-coumarin (L). The ligand, L, reacts with Cu(MeCN)4]ClO4/AgNO3 to synthesize Cu(I) and Ag(I) complexes of formulae, Cu(L)2]ClO4 and Ag(L)2]NO3, respectively. While similar reaction in the presence of PPh3 has isolated Cu(L)(PPh3)2]ClO4 and Ag(L)(PPh3)2]NO3. All these compounds are characterized by FTIR, UV-Vis and 1H NMR spectroscopic data. In case of Cu(L)(PPh3)2]ClO4 and Ag(L)(PPh3)2]NO3, the structures have been confirmed by X-ray crystallography. The structure of the complexes are distorted tetrahedral in which L coordinates in a N,N′ bidentate fashion and other two coordination sites are occupied by PPh3. The ligand and the complexes are fluorescent and the fluorescence quantum yields of Cu(L)(PPh3)2]ClO4 and Ag(L)(PPh3)2]NO3 are higher than Cu(L)2]ClO4 and Ag(L)2]NO3. Cu(I) complexes show Cu(II)/Cu(I) quasireversible redox couple while Ag(I) complexes exhibit deposition of Ag(0) on the electrode surface during cyclic voltammetric experiments. gaussian 03 computations of representative complexes have been used to determine the composition and energy of molecular levels. An attempt has been made to explain solution spectra and redox properties of the complexes. |
| Keywords: | N-[(2-Pyridyl)methyliden]-6-coumarin Copper(I) Silver(I) Structures and spectra Electrochemistry Density functional theory (DFT) |
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