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    • Keywords


      Density functional theory; global and local reactivity descriptors; NMR; UV-Vis; lanthanides.

    • Abstract


      Complexation study of acetohydroxamic (AHA) ligand with La(III), Nd(III), Eu(III), Er(III), andLu(III), as representative of lanthanide (Ln) series, has been described, in presence of pure nitrate andcombination of nitrate and perchlorate ions using various spectroscopic analysis and density functional theory(DFT) calculations. Nuclear magnetic resonance (NMR) spectroscopy reports the bidentate mode of coordinationof Z-Keto tautomer of AHA monomer with La(III). Formation of 1:3 Nd(III)-AHA complexes inpresence of pure nitrate and a combination of nitrate and perchlorate ions has been observed from ultravioletvisible(UV-Vis) spectroscopy analysis. The geometrical parameter analysis exhibit the bidentate modecoordination fashion of the AHA monomer which corroborates the NMR results. The geometrical parameter,frontier orbital(HOMO-LUMO), global reactivity descriptors and local reactivity descriptors analysis supportsthe findings of the spectroscopy titration methods that stability of Ln-AHA complexes decreases in thepresence of pure nitrate ions than in presence of both perchlorate and nitrate ions. The trend of theoreticalNMR chemical shifts of AHA and La(III)-AHA complexes support the experimental NMR chemical shifts.This work helps to measure subtle differences in complexation behaviour of AHA with Ln in presence of purenitrate and a combination of nitrate and perchlorate ions quantitatively, providing information about the Ln-AHA structural environment.

    • Graphical Abstract


      Various spectroscopic methods (UV-Vis, NMR, and Fluorescence spectroscopy) and density functional theory (DFT) calculations have been implemented for structural characterization of lanthanides (Ln(III))-acetohydroxamic acid(AHA) complexes in the presence of a combination of both perchlorate and nitrate ions and in pure nitrate ions. The Ln(III)-AHA complexes show more stability in the presence of a combination of both perchlorate and nitrate ions than in the presence of nitrate ions which is supported by DFT calculations.

    • Author Affiliations



      1. Department of Metallurgical and Materials Engineering, Indian Institute of Technology Kharagpur, Kharagpur 721302, West Bengal, India
      2. Radiochemistry Division, Trombay, Bhabha Atomic Research Centre, BARC, Mumbai 400085, Maharashtra, India
    • Dates

  • Journal of Chemical Sciences | News

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