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Chelating effect of alizarin-oxalate on La3+ and Nd3+ in acidic, basic and neutral medium: a DFT study

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Abstract

This study focuses on conducting a comparative study of the extraction capacities of alizarin-oxalate (AR-Ox) ligands with La3+ and Nd3+ in acidic, neutral, and alkaline mediums. Density functional theory calculations at ωB97X-D/6-311++G(d,p)/SDD level have been performed for structural, thermochemical, frontier-orbital (highest occupied molecular orbitals and lowest unoccupied molecular orbitals), natural bond orbital, reduced density gradient (RDG), and density of state analysis for alizarin-oxalate-La(III) (AR-Ox-La) and alizarin-oxalate-Nd(III) (AR-Ox-Nd) complexes. The bonding characteristics of La3+ & Nd3+ ions with alizarin-oxalate ligand have been analysed using the quantum theory of atoms in molecules, revealing the presence of an intermediate type of bond between closed-shell and shared-shell electrons in (La/Nd)-O, (La/Nd)-C. The reduced density gradient (RDG) and iso-surface generated through the Multiwfn program shows mostly hydrogen-like and van der Waals interaction between La3+/Nd3+ and oxygen atoms of alizarin-oxalate ligand except for some of the complexes showing the presence of non-bonded/repulsive (La/Nd)-O interaction. Thermochemical, DOS, and natural bond orbital analysis reveals alizarin-oxalate-(La3+/Nd3+) complexes in the alkaline medium is more stable than in neutral and acidic medium, and the stability of AR-Ox-Nd complexes is more than AR-Ox-La complexes. It is observed that participation of oxygen atoms from both alizarin and oxalate in bond formation with lanthanides enhances the stability of alizarin-oxalate-lanthanide complexes, emphasizing the pivotal role of ligand coordination modes. This work illustrates the subtle differences in chelating properties of alizarin-oxalate ligands with La3+ and Nd3+ for designing new ligands for efficient selective lanthanide separation.

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Authors and Affiliations

  1. Department of Metallurgical and Materials Engineering, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal, 721302, India

    Anindita Pati & T. K. Kundu

  2. Department of Metallurgical and Materials Engineering, Indian Institute of Engineering Science and Technology, Howrah, West Bengal, 711103, India

    Snehanshu Pal

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Contributions

Anindita Pati: Performed all the DFT calculations, analysed data and wrote the manuscript. Snehanshu Pal: Supervised and reviewed all the DFT calculations and data. Tarun Kumar Kundu: Supervised and reviewed the entire work and shared valuable comments to finalize the manuscript.

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Correspondence to T. K. Kundu.

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Pati, A., Kundu, T.K. & Pal, S. Chelating effect of alizarin-oxalate on La3+ and Nd3+ in acidic, basic and neutral medium: a DFT study. Theor Chem Acc 143, 21 (2024). https://doi.org/10.1007/s00214-024-03094-0

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