Jump to main content
Jump to site search

Issue 41, 2015
Previous Article Next Article

Four-coordinate nickel(II) and copper(II) complex based ONO tridentate Schiff base ligands: synthesis, molecular structure, electrochemical, linear and nonlinear properties, and computational study

Author affiliations

Abstract

We report the synthesis, characterization, crystal structures, nonlinear-optical (NLO) properties, and density functional theory (DFT) calculations of nickel(II) and copper(II) complex based ONO tridentate Schiff base ligands: two mononuclear compounds, [Ni(An-ONO)(NC5H5)] (5) and [Cu(An-ONO)(4-NC5H4C(CH3)3)] (6), and two heterobimetallic species, [M(Fc-ONO)(NC5H5)] (M = Ni, 7; Cu, 8), where An-ONOH2 (3) and Fc-ONOH2 (4) are the 1 : 1 condensation products of 2-aminophenol and p-anisoylacetone and ferrocenoylacetone, respectively. These compounds were characterised by microanalysis, FT-IR and X-ray crystallography in the solid state and in solution by UV-vis and 1H and 13C NMR spectroscopy. The crystal structures of 3–5, 7 and 8 have been determined and show for Schiff base complexes 5, 7 and 8 a four-coordinated square-planar environment for nickel and copper ions. The electrochemical behavior of all derivatives 3–8 was investigated by cyclic voltammetry in dichloromethane, and discussed on the basis of DFT-computed electronic structures of the neutral and oxidized forms of the compounds. The second-order NLO responses of 3–8 have been determined by harmonic light scattering measurements using a 10−2 M solution of dichloromethane and working with a 1.91 μm incident wavelength, giving rather high β1.91 values of 350 and 290 × 10−30 esu for the mononuclear species 5 and 6, respectively. The assignment and the nature of the electronic transitions observed in the UV-vis spectra were analyzed using time-dependent (TD) DFT calculations. They are dominated by LMCT, MLCT and π–π* transitions.

Graphical abstract: Four-coordinate nickel(ii) and copper(ii) complex based ONO tridentate Schiff base ligands: synthesis, molecular structure, electrochemical, linear and nonlinear properties, and computational study

Back to tab navigation

Supplementary files

Publication details

The article was received on 23 Jul 2015, accepted on 14 Sep 2015 and first published on 14 Sep 2015


Article type: Paper
DOI: 10.1039/C5DT02822A
Author version
available:
Download author version (PDF)
Citation: Dalton Trans., 2015,44, 18019-18037
  •   Request permissions

    Four-coordinate nickel(II) and copper(II) complex based ONO tridentate Schiff base ligands: synthesis, molecular structure, electrochemical, linear and nonlinear properties, and computational study

    N. Novoa, T. Roisnel, P. Hamon, S. Kahlal, C. Manzur, H. M. Ngo, I. Ledoux-Rak, J. Saillard, D. Carrillo and J. Hamon, Dalton Trans., 2015, 44, 18019
    DOI: 10.1039/C5DT02822A

Search articles by author

Spotlight

Advertisements