An efficient ab initio DFT and PCM assessment of the potentiometric selectivity of a salophen type Schiff base

Demir S., Yilmaz H., Dilimulati M., Andaç M.

JOURNAL OF MOLECULAR MODELING, vol.20, no.6, 2014 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 20 Issue: 6
  • Publication Date: 2014
  • Doi Number: 10.1007/s00894-014-2258-9
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Keywords: DFT, Membrane electrode, PCM, Potentiometric selectivity, Salophen, ELECTRODE, ION, COMPLEXES, HYDRATION, SOLUTES, CATIONS
  • Ondokuz Mayıs University Affiliated: Yes


As a neutral carrier component for the preparation of a potentiometric membrane sensor, the affinity and selectivity of the salophen type Schiff base ligand obtained by 1: 2 condensation of 2.3-diaminopyridine with salicylaldehyde toward a series of common cations has been fully examined by DFT/B3LYP and integral equation formalism polarizable continum model (IEF-PCM or only given with PCM as default input in the computations) in combination with the experimental data. Both the potentiometric measurements and DFT calculations have exhibited that the ionophore shows appreciable selectivity for Cu2+ ion over other cations. Four different approaches where the last three are the modified version of each other have been evaluated and compared with potentiometric data. Based upon the results of comparison among the approaches suggested to verify the selective behavior of ionophore toward Cu2+, PCM implemented approach having a whole computational groundwork has given well-matched results with the observed data and with the method augmented with experimental hydration energies. The foremost interferences were detected by determining potentiometric selectivity coefficients for each metal ion relative to Cu2+ and compared to the results obtained by the DFT calculations.