Uptake of Am(III) Ions and Eu(III) Ions Using Cyclic Substituted N, O‐hybrid 1, 10‐Phenanthroline Derived Phosphine Oxide Ligands ‐ A DFT Exploration. Issue 17 (3rd May 2022)

• Record Type: Journal Article
• Authors: Ebenezer, Cheriyan; Solomon, Rajadurai Vijay
• Is Part Of: ChemistrySelect. Volume 7:Issue 17(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-05-03
• Subjects: Phenanthroline -- Phosphine oxide ligand -- Computational chemistry -- N ligands, Am (III)/Eu (III) uptake; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.202200446
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: The spent nuclear fuel has radioactive species such as actinides and lanthanides which hamper its reprocessing. This issue is undertaken by designing suitable organic ligands to strip off actinides from lanthanides. Due to the versatility of phenanthroline‐derived N, O‐donor ligands, we have looked into the electronic structure of N, O‐hybrid 1, 10‐phenanthroline derived phosphine oxide ligands with various cyclic substitutions. The complexation behavior of these ligands with Am(III) and Eu(III) is evaluated using density functional theory calculations. Electronic structures divulge that in all these tetra‐coordinated complexes, the oxygen atoms bind strongly than the nitrogen atoms. The substitution of a benzene ring on the phosphorus increases the selectivity whereas the binding is enhanced by the substitution of cyclopentane. QTAIM analysis portrays the weak C−H−O interactions present in these complexes. Energy decomposition analysis in gas and solvent phases estimates the weak stabilizing interactions in these complexes. All the calculations bring out the salient structural features of these ligands which will further enrich our understanding of the tailoring of ligands for efficient uptake of Am (III) ions over Eu (III) ions. Abstract : Substitution of a benzene ring on the phosphorus increases the selectivity to strip radioactive Am(III) over Eu(III). The binding towards Am(III) and Eu(III) is enhanced by the substitution of cyclopentane on the phosphorus. Electronic structures reveal that in all these tetra‐coordinated complexes, M−O bonds are stronger than the M−N bonds. Am complexes, the orbital interactions play a key role in the total binding energy whereas in Eu complexes electrostatic interactions play an significant role towards the total binding energy.