“Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands

Ellis, Ross J.; Brigham, Derek M.; Delmau, Laetitia; Ivanov, Alexander S.; Williams, Neil J.; Vo, Minh Nguyen; Reinhart, Benjamin; Moyer, Bruce A.; Bryantsev, Vyacheslav S.

doi:10.1021/acs.inorgchem.6b02156

Title: “Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands

Journal Article · Wed Nov 23 00:00:00 EST 2016 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.6b02156· OSTI ID:1394549

; Brigham, Derek M.; Delmau, Laetitia; Ivanov, Alexander S.; Williams, Neil J.; Vo, Minh Nguyen; Reinhart, Benjamin; Moyer, Bruce A.;

The subtle energetic differences underpinning adjacent lanthanide discrimination are explored with diglycolamide ligands. Our approach converges liquid–liquid extraction experiments with solution-phase X-ray absorption spectroscopy (XAS) and density functional theory (DFT) simulations, spanning the lanthanide series. The homoleptic [(DGA)3Ln]3+ complex was confirmed in the organic extractive solution by XAS, and this was modeled using DFT. An interplay between steric strain and coordination energies apparently gives rise to a nonlinear trend in discriminatory lanthanide ion complexation across the series. Our results highlight the importance of optimizing chelate molecular geometry to account for both coordination interactions and strain energies when designing new ligands for efficient adjacent lanthanide separation for rare-earth refining.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Advanced Manufacturing Office

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1394549

Journal Information:: Inorganic Chemistry, Vol. 56, Issue 3; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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The lanthanide contraction effect and organic additives impact the coordination structures of lanthanide ions with symmetrical octamethyl-substituted cucurbit[6]uril ligands Lin, Rui-Lian; Zhou, Jia-Jia; Zhou, Fu Hou CrystEngComm, Vol. 21, Issue 37 https://doi.org/10.1039/c9ce00812h	journal	January 2019
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Synergistic Extraction of Lanthanides (III) with Mixtures of TODGA and Hydrophobic Ionic Liquid into Molecular Diluent Turanov, A. N.; Karandashev, V. K.; Khvostikov, V. A. Solvent Extraction and Ion Exchange, Vol. 35, Issue 7 https://doi.org/10.1080/07366299.2017.1355170	journal	September 2017
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