# Insights into the Green Solvent Extraction and Selectivity of 4f-Ions by Chelating Ligands Comprised of Pyrazolone and Carboxymethyl-Bridged Saturated N-Heterocyclic Moieties

## TL;DR

The paper introduces a new green solvent system for efficiently extracting rare earth ions using chelating ligands with specific structural features.

## Contribution

The study demonstrates a novel intramolecular cooperative effect in ionic liquid solvents that enhances the extraction efficiency of Ln3+ ions.

## Key findings

- The chelating ligands with β-dicarbonyl and N-heterocyclic units show improved extraction performance in ionic liquids compared to chloroform.
- The intramolecular cooperative effect is influenced by the compatibility between metal ion size and ligand cavity flexibility.
- The system effectively extracts refractory and platinum group metals in various organic solvents.

## Abstract

A new solvent extraction system for the removal of 4f ions (Ln3+) from water by use of chelating ligands (HLn, n = 5, 6, 7, and 8) composed of heterocyclic receptors and one β-dicarbonyl fragment is reported. The covalent attachment of a β-dicarbonyl unit to a saturated N-heterocycle with variable ring size resulted in a cooperative interaction within the receptor for Ln3+ transfer, which remarkably enhanced the efficiency of the process. The intramolecular cooperative effect was observed only in the ionic liquid (IL) solvent system, providing a several-fold increase in extraction performance for Ln3+ ions (La, Nd, Eu and Dy) over chloroform. Thus, it is not possible to confirm that an identical reaction mechanism operated in both liquid systems: IL or CHCl3. The existence of neutral chelates of the type LnL3 or anionic lanthanoid complexes [LnL4−] in an ionic medium during the solvent extraction process applying various solvent systems has been established hitherto. Consequently, the Ln3+ ion was held by HLn molecules more rigidly in an IL medium ([C1Cnim+]/[C1C4pyr+]/[C1C4pip+][Tf2N−], n = 4, 6, 8, 10) than in chloroform, representing an important factor dominating the magnitude of the intramolecular cooperative effect of the chelating ligands for Ln3+ ions. The effect of the diluent’s chemical nature on the metal extraction and separation has been studied and discussed thoroughly. Furthermore, competitive solvent extraction and separation studies with various s-, p-, d-, and f-ions of the periodic table revealed that the magnitude of the intramolecular cooperative effect depends on the suitability between the metal ion size and the cavity size or flexibility of the HLn compounds. In addition, the solvent extraction process of 12 refractory metals and 8 platinum group metals with the synthesized chelating extractants is also investigated in different organic liquid media.