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SM ISO690:2012 GRĂDINARU, Julieta, FORNI, Alessandra, DRUŢĂ, Vadim, TESSORE, Francesca, ZECCHIN, Sandro, QUICI, Silvio, GERBELEU, Nicolae. Structural, spectral, electric-field-induced second harmonic, and theoretical study of Ni(II), Cu(II), Zn(II), and VO(II) complexes with [N 2O2] unsymmetrical Schiff bases of S- methylisothiosemicarbazide derivatives. In: Inorganic Chemistry, 2007, vol. 46, pp. 884-895. ISSN 0020-1669. DOI: https://doi.org/10.1021/ic062035r |
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Inorganic Chemistry | |
Volumul 46 / 2007 / ISSN 0020-1669 | |
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DOI:https://doi.org/10.1021/ic062035r | |
Pag. 884-895 | |
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Rezumat | |
New unsymmetrical [N2O2] tetradentate Schiff base complexes of Ni(II), Cu(II), Zn(II), and VO(II) were synthesized by template condensation of the tetradentate precursor 1-phenylbutane-1,3-dione mono-S-methylisothiosemicarbazone with o-hydroxybenzaldehyde or its 5-phenylazo derivative. They were characterized by elemental analysis, IR, UV-vis, electron spin resonance, and NMR spectroscopy, mass spectrometry, and magnetic measurements. The crystal structures of five of them have been determined by X-ray diffraction using, in some cases, synchrotron radiation. These compounds are characterized by a large thermal stability; their decomposition temperatures range from 240 up to 310°C. Complexes with the phenylazo substituent were found to possess a large second-order nonlinear optical (NLO) response, as determined both by measurements of solution-phase direct current electric-field-induced second harmonic generation and by theoretical time-dependent density functional theory (TDDFT) calculations. The molecular hyperpolarizability was found to decrease in the order Zn(II) > Cu(II) > Ni(II) ∼ VO(II). The active role of the metal in determining the NLO properties of the complexes was shown through an analysis of their UV-vis spectra, which revealed the presence of metal-to-ligand (in closed-shell complexes) and ligand-to-metal (in open-shell complexes) charge-transfer bands together with intra-ligand charge-transfer transitions. Assignment of the bands was based on the analysis of the TDDFT computed spectra |
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