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

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.
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [2] ;  [3] ;  [1] ;  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 3; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Critical Materials Institute (CMI)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1362226

Ellis, Ross J., Brigham, Derek M., Delmau, Laetitia, Ivanov, Alexander S., Williams, Neil J., Univ. of Tennessee, Knoxville, TN, Vo, Minh Nguyen, Univ. of Pittsburgh, PA, Reinhart, Benjamin, Moyer, Bruce A., and Bryantsev, Vyacheslav S.. “Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands. United States: N. p., Web. doi:10.1021/acs.inorgchem.6b02156.
Ellis, Ross J., Brigham, Derek M., Delmau, Laetitia, Ivanov, Alexander S., Williams, Neil J., Univ. of Tennessee, Knoxville, TN, Vo, Minh Nguyen, Univ. of Pittsburgh, PA, Reinhart, Benjamin, Moyer, Bruce A., & Bryantsev, Vyacheslav S.. “Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands. United States. doi:10.1021/acs.inorgchem.6b02156.
Ellis, Ross J., Brigham, Derek M., Delmau, Laetitia, Ivanov, Alexander S., Williams, Neil J., Univ. of Tennessee, Knoxville, TN, Vo, Minh Nguyen, Univ. of Pittsburgh, PA, Reinhart, Benjamin, Moyer, Bruce A., and Bryantsev, Vyacheslav S.. 2016. "“Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands". United States. doi:10.1021/acs.inorgchem.6b02156. https://www.osti.gov/servlets/purl/1362226.
@article{osti_1362226,
title = {“Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands},
author = {Ellis, Ross J. and Brigham, Derek M. and Delmau, Laetitia and Ivanov, Alexander S. and Williams, Neil J. and Univ. of Tennessee, Knoxville, TN and Vo, Minh Nguyen and Univ. of Pittsburgh, PA and Reinhart, Benjamin and Moyer, Bruce A. and Bryantsev, Vyacheslav S.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.6b02156},
journal = {Inorganic Chemistry},
number = 3,
volume = 56,
place = {United States},
year = {2016},
month = {11}
}