Due to the ever-increasing demand for high-purity individual rare-earth elements, novel and highly selective separation processes are increasingly sought after. Herein, we report a separation protocol that employs shape-persistent 2,9-bis-lactam-1,10-phenanthroline (BLPhen) ligands exhibiting unparalleled selectivity for light trivalent lanthanides. The highly preorganised binding pockets of the ligands allowed for the separation of lanthanides with high fidelity, even in the presence of competing transition metals, in a biphasic separation system. Notably, the selectivity trends of the BLPhen ligands towards metal ions across the lanthanide series can be chemically modulated by altering the molecular rigidity of the extractant.
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Completely preorganized bis-lactam-1,10-phenanthroline ligands with high stability for efficient separation of Am(III) over Eu(III).
Dalton Trans
January 2025
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China.
N,O-Heterocyclic ligands such as 2,9-diamide-1,10-phenanthroline dicarboxamide (DAPhen) and bis-lactam-1,10-phenanthroline (BLPhen) exhibit excellent separation performance for Am(III) and Eu(III) in high-level liquid waste. However, DAPhen-based ligands show poor extraction capacity, and BLPhen ligands suffer from decomposition in acidic solutions, which hinders their application in practical separation processes. To develop ligands with superior performance, two new completely preorganized and highly stabilized bis-lactam-1,10-phenanthroline (BLPhen) ligands with varying alkyl chain lengths were synthesized, demonstrating exceptional extraction and separation of Am(III) from Eu(III) with maximum separation factors of 68 and 53, respectively.
View Article and Find Full Text PDFN-oxide ligands for selective separations of lanthanides: insights from computation.
RSC Adv
January 2023
Department of Chemical and Biomolecular Engineering, Vanderbilt University Nashville TN 37235 USA
Preorganized ligands such as bis-lactam-1,10-phenanthroline (BLPhen) show unique selectivity trends across the lanthanide series, indicating the synergistic effects of both N and O donors in complexing with lanthanides. We hypothesize that by replacing amide functional groups with an N-oxide functionality would open the door to new ligand architectures with improved selectivities. To test this idea, we computationally examined mixed N,O-donor ligands containing pyridinic N and N-oxide groups and evaluated their relative aqueous La(iii)/Ln(iii) selectivity by computing free energy changes for the exchange reaction between the designed ligands and a reference ligand.
View Article and Find Full Text PDFAtomistic Insights into Structure and Dynamics of Neodymium(III) Complexation with a Bis-lactam Phenanthroline Ligand in the Organic Phase.
ACS Omega
June 2022
Department of Chemistry, University of California, Riverside, California 92521, United States.
Rare-earth elements (REEs) such as neodymium are critical materials needed in many important technologies, and rigid neutral bis-lactam-1,10-phenanthroline (BLPhen) ligands show one of the highest extraction performance for complexing Nd(III) in REE uptake and separation processes. However, the local structure of the complexes formed between BLPhen and Nd(III) in a typical organic solvent such as dichloroethane (DCE) is unclear. Here, we perform first-principles molecular dynamics (FPMD) simulations to unveil the structure of complexes formed by BLPhen with Nd(NO) in the DCE solvent.
View Article and Find Full Text PDFEfficient Separation of Light Lanthanides(III) by Using Bis-Lactam Phenanthroline Ligands.
Chemistry
May 2019
Chemical Sciences Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37831-6119, USA.
Due to the ever-increasing demand for high-purity individual rare-earth elements, novel and highly selective separation processes are increasingly sought after. Herein, we report a separation protocol that employs shape-persistent 2,9-bis-lactam-1,10-phenanthroline (BLPhen) ligands exhibiting unparalleled selectivity for light trivalent lanthanides. The highly preorganised binding pockets of the ligands allowed for the separation of lanthanides with high fidelity, even in the presence of competing transition metals, in a biphasic separation system.
View Article and Find Full Text PDFBis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency.
Inorg Chem
May 2017
Chemical Sciences Division, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
We report a new family of preorganized bis-lactam-1,10-phenanthroline (BLPhen) complexants that possess both hard and soft donor atoms within a convergent cavity and show unprecedented extraction strength for the trivalent f-block metal ions. BLPhen ligands with saturated and unsaturated δ-lactam rings have notable differences in their affinity and selectivity for Am(III) over Eu(III), with the latter being the most selective mixed N,O-donor extractant of Am(III) reported to date. Saturated BLPhen was crystallized with five Ln(III) nitrates to form charge-neutral 1:1 complexes in the solid state.
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