This content will become publicly available on Thu Jul 11 00:00:00 EDT 2024
Changes in nitrate binding with lanthanides in BLPhen complexes
Abstract
Preorganized ligands such as bis-lactam-1,10-phenanthroline (BLPhen) offer unique selectivity trends in solvent extraction of rare-earth ions, particularly from aqueous nitrate solutions. However, due to the ligand’s lipophilicity it is experimentally challenging to obtain crystal structures of the corresponding lanthanide (Ln):ligand complexes to describe the local structure of the first coordination shell and the role of the nitrate ions in the organic phase. In this work, we report first principles molecular dynamics (FPMD) simulations of the complexation of trivalent lanthanide ions (La, Nd, and Eu) with the BLPhen ligand in the presence of nitrate ions in the dichloroethane (DCE) solvent. We find that two nitrate anions are present in the first solvation shell and the third nitrate anion is far from the first solvation shell in all three [Ln(BLPhen)2]3+ complexes examined. Moving along the lanthanide series from La to Nd to Eu, the binding pocket formed by the two BLPhen ligands shrinks in size; as a result, the two nitrate configuration changes from one-monodentate/one-bidentate binding mode for La and Nd to all monodentate for Eu. Meanwhile, the total coordination number drops from 11 for La and Nd to 10 for Eu. More interestingly, the bidentate binding in [La(BLPhen)2]3+ and [Nd(BLPhen)2]3+ complexesmore »
- Authors:
-
[2];
[2];
[3]
- Univ. of California, Riverside, CA (United States)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Vanderbilt Univ., Nashville, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1995657
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Molecular Liquids
- Additional Journal Information:
- Journal Volume: 387; Journal ID: ISSN 0167-7322
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Solvent extraction; Rare earth separations; First principles molecular dynamics; Solvation; Lanthanides
Citation Formats
Reddy, Th. Dhileep N., Ivanov, Alexander S., Driscoll, Darren M., Jansone-Popova, Santa, and Jiang, De-en. Changes in nitrate binding with lanthanides in BLPhen complexes. United States: N. p., 2023.
Web. doi:10.1016/j.molliq.2023.122573.
Reddy, Th. Dhileep N., Ivanov, Alexander S., Driscoll, Darren M., Jansone-Popova, Santa, & Jiang, De-en. Changes in nitrate binding with lanthanides in BLPhen complexes. United States. https://doi.org/10.1016/j.molliq.2023.122573
Reddy, Th. Dhileep N., Ivanov, Alexander S., Driscoll, Darren M., Jansone-Popova, Santa, and Jiang, De-en. Tue .
"Changes in nitrate binding with lanthanides in BLPhen complexes". United States. https://doi.org/10.1016/j.molliq.2023.122573.
@article{osti_1995657,
title = {Changes in nitrate binding with lanthanides in BLPhen complexes},
author = {Reddy, Th. Dhileep N. and Ivanov, Alexander S. and Driscoll, Darren M. and Jansone-Popova, Santa and Jiang, De-en},
abstractNote = {Preorganized ligands such as bis-lactam-1,10-phenanthroline (BLPhen) offer unique selectivity trends in solvent extraction of rare-earth ions, particularly from aqueous nitrate solutions. However, due to the ligand’s lipophilicity it is experimentally challenging to obtain crystal structures of the corresponding lanthanide (Ln):ligand complexes to describe the local structure of the first coordination shell and the role of the nitrate ions in the organic phase. In this work, we report first principles molecular dynamics (FPMD) simulations of the complexation of trivalent lanthanide ions (La, Nd, and Eu) with the BLPhen ligand in the presence of nitrate ions in the dichloroethane (DCE) solvent. We find that two nitrate anions are present in the first solvation shell and the third nitrate anion is far from the first solvation shell in all three [Ln(BLPhen)2]3+ complexes examined. Moving along the lanthanide series from La to Nd to Eu, the binding pocket formed by the two BLPhen ligands shrinks in size; as a result, the two nitrate configuration changes from one-monodentate/one-bidentate binding mode for La and Nd to all monodentate for Eu. Meanwhile, the total coordination number drops from 11 for La and Nd to 10 for Eu. More interestingly, the bidentate binding in [La(BLPhen)2]3+ and [Nd(BLPhen)2]3+ complexes is highly dynamic, frequently switching to monodentate and back. The FPMD insights into the differing modes and dynamics of nitrates in the first coordination shell will be useful for further atomistic understanding of the complex structure, formation, and stability in the organic phase.},
doi = {10.1016/j.molliq.2023.122573},
journal = {Journal of Molecular Liquids},
number = ,
volume = 387,
place = {United States},
year = {Tue Jul 11 00:00:00 EDT 2023},
month = {Tue Jul 11 00:00:00 EDT 2023}
}
Free Publicly Available Full Text
This content will become publicly available on July 11, 2024
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Theoretical Insights into Transplutonium Element Separation with Electronically Modulated Phenanthroline-Derived Bis-Triazine Ligands
journal, July 2021
- Liu, Yang; Wang, Cong-Zhi; Wu, Qun-Yan
- Inorganic Chemistry, Vol. 60, Issue 14
A Computational Approach to Predicting Ligand Selectivity for the Size-Based Separation of Trivalent Lanthanides: A Computational Approach to Predicting Ligand Selectivity for the Size-Based Separation of Trivalent Lanthanides
journal, June 2016
- Ivanov, Alexander S.; Bryantsev, Vyacheslav S.
- European Journal of Inorganic Chemistry, Vol. 2016, Issue 21
Noncoordinating Secondary Sphere Ion Modulates Supramolecular Clustering of Lanthanides
journal, December 2022
- Driscoll, Darren M.; Liu, Hongjun; Reinhart, Benjamin
- The Journal of Physical Chemistry Letters, Vol. 13, Issue 51
Lanthanide Chemistry: From Coordination in Chemical Complexes Shaping Our Technology to Coordination in Enzymes Shaping Bacterial Metabolism
journal, September 2016
- Martinez-Gomez, Norma Cecilia; Vu, Huong N.; Skovran, Elizabeth
- Inorganic Chemistry, Vol. 55, Issue 20
Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes
journal, February 2009
- Rao, Linfeng; Tian, Guoxin
- Inorganic Chemistry, Vol. 48, Issue 3
Understanding the Binding of a Bifunctional Amidoximate–Carboxylate Ligand with Uranyl in Seawater
journal, November 2018
- Priest, Chad; Li, Bo; Jiang, De-en
- The Journal of Physical Chemistry B, Vol. 122, Issue 50
Highly Efficient Separation of Actinides from Lanthanides by a Phenanthroline-Derived Bis-triazine Ligand
journal, August 2011
- Lewis, Frank W.; Harwood, Laurence M.; Hudson, Michael J.
- Journal of the American Chemical Society, Vol. 133, Issue 33
Structural study of lanthanides(III) in aqueous nitrate and chloride solutions by EXAFS
journal, February 1999
- Yaita, T.; Narita, H.; Suzuki, Sh.
- Journal of Radioanalytical and Nuclear Chemistry, Vol. 239, Issue 2
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater
journal, November 2017
- Ivanov, Alexander S.; Leggett, Christina J.; Parker, Bernard F.
- Nature Communications, Vol. 8, Issue 1
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Strong Periodic Tendency of Trivalent Lanthanides Coordinated with a Phenanthroline-Based Ligand: Cascade Countercurrent Extraction, Spectroscopy, and Crystallography
journal, June 2021
- Yang, Xiao-Fan; Ren, Peng; Yang, Qi
- Inorganic Chemistry, Vol. 60, Issue 13
Selective crystallization of dysprosium complex from neodymium/dysprosium mixture enabled by cooperation of coordination and crystallization
journal, January 2022
- Masuya-Suzuki, Atsuko; Hosobori, Koji; Sawamura, Ryota
- Chemical Communications, Vol. 58, Issue 14
Unusual structure, bonding and properties in a californium borate
journal, March 2014
- Polinski, Matthew J.; Garner, Edward B.; Maurice, Rémi
- Nature Chemistry, Vol. 6, Issue 5
A novel highly selective ligand for separation of actinides and lanthanides in the nuclear fuel cycle. Experimental verification of the theoretical prediction
journal, January 2017
- Lavrov, H. V.; Ustynyuk, N. A.; Matveev, P. I.
- Dalton Transactions, Vol. 46, Issue 33
First-principles molecular dynamics simulation of the Ca 2 UO 2 (CO 3 ) 3 complex in water
journal, January 2016
- Priest, Chad; Tian, Ziqi; Jiang, De-en
- Dalton Transactions, Vol. 45, Issue 24
Syntheses and Characterization of Tetrazolate-Based Lanthanide Compounds and Selective Crystallization Separation of Neodymium and Dysprosium
journal, November 2022
- Bai, Zhuanling; Scheibe, Benjamin; Sperling, Joseph M.
- Inorganic Chemistry, Vol. 61, Issue 48
Atomistic Insights into Structure and Dynamics of Neodymium(III) Complexation with a Bis-lactam Phenanthroline Ligand in the Organic Phase
journal, June 2022
- Reddy, Th. Dhileep N.; Ivanov, Alexander S.; Driscoll, Darren M.
- ACS Omega, Vol. 7, Issue 24
Uranyl–Glutardiamidoxime Binding from First-Principles Molecular Dynamics, Classical Molecular Dynamics, and Free-Energy Simulations
journal, July 2017
- Priest, Chad; Li, Bo; Jiang, De-en
- Inorganic Chemistry, Vol. 56, Issue 16
Efficient Separation of Light Lanthanides(III) by Using Bis‐Lactam Phenanthroline Ligands
journal, March 2019
- Healy, Mary R.; Ivanov, Alexander S.; Karslyan, Yana
- Chemistry – A European Journal, Vol. 25, Issue 25
Bis-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
journal, April 2017
- Jansone-Popova, Santa; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.
- Inorganic Chemistry, Vol. 56, Issue 10
Theoretical Insights into Phenanthroline-Based Ligands toward the Separation of Am(III)/Eu(III)
journal, September 2022
- Zou, Yao; Lan, Jian-Hui; Yuan, Li-Yong
- Inorganic Chemistry, Vol. 61, Issue 39
Interaction of trivalent lanthanide cations with nitrate anions: a quantum chemical investigation of monodentate/bidentate binding modes
journal, October 2001
- Dobler, Marc; Guilbaud, Philippe; Dedieu, Alain
- New Journal of Chemistry, Vol. 25, Issue 11
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
A critical review on solvent extraction of rare earths from aqueous solutions
journal, February 2014
- Xie, Feng; Zhang, Ting An; Dreisinger, David
- Minerals Engineering, Vol. 56
Lanthanide–tetrapyrrole complexes: synthesis, redox chemistry, photophysical properties, and photonic applications
journal, January 2021
- Chan, Wai-Lun; Xie, Chen; Lo, Wai-Sum
- Chemical Society Reviews, Vol. 50, Issue 21
TRAVIS—A free analyzer for trajectories from molecular simulation
journal, April 2020
- Brehm, M.; Thomas, M.; Gehrke, S.
- The Journal of Chemical Physics, Vol. 152, Issue 16
Complexation behavior of trivalent actinides and lanthanides with 1,10-phenanthroline-2,9-dicarboxylic acid based ligands: insight from density functional theory
journal, January 2012
- Manna, Debashree; Ghanty, Tapan K.
- Physical Chemistry Chemical Physics, Vol. 14, Issue 31
Liquid-liquid extraction of rare-earth elements from aqueous acid solutions by acid organophosphorus compounds
journal, June 1989
- Sato, Taichi
- Hydrometallurgy, Vol. 22, Issue 1-2
Theoretical insights into the substitution effect of phenanthroline derivative ligands on the extraction of Mo (VI)
journal, January 2022
- Zhang, Si-Mei; Wu, Qun-Yan; Yuan, Li-Yong
- Separation and Purification Technology, Vol. 280
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Complexation of Lanthanides and Heavy Actinides with Aqueous Sulfur-Donating Ligands
journal, April 2021
- Bessen, Nathan P.; Popov, Ivan A.; Heathman, Colt R.
- Inorganic Chemistry, Vol. 60, Issue 9
Interactions between lanthanide cations and nitrate anions in water. Part 1.—Effect of the ionic strength on the Gibbs energy, enthalpy and entropy of complexation of the neodymium cation
journal, January 1996
- Bonal, Christine; Morel, Jean-Pierre; Morel-Desrosiers, Nicole
- J. Chem. Soc., Faraday Trans., Vol. 92, Issue 24
Molecular Dynamics Simulations of Complexation of Am(III) with a Preorganized Dicationic Ligand in an Ionic Liquid
journal, July 2021
- Singh, Meena B.; Fu, Yuqing; Popovs, Ilja
- The Journal of Physical Chemistry B, Vol. 125, Issue 30
High-Frequency and -Field Electron Paramagnetic Resonance Spectroscopic Analysis of Metal–Ligand Covalency in a 4f 7 Valence Series (Eu 2+ , Gd 3+ , and Tb 4+ )
journal, June 2021
- Gompa, Thaige P.; Greer, Samuel M.; Rice, Natalie T.
- Inorganic Chemistry, Vol. 60, Issue 12
Rare earth elements: Mendeleev’s bane, modern marvels
journal, January 2019
- Cheisson, Thibault; Schelter, Eric J.
- Science, Vol. 363, Issue 6426
TRAVIS - A Free Analyzer and Visualizer for Monte Carlo and Molecular Dynamics Trajectories
journal, July 2011
- Brehm, Martin; Kirchner, Barbara
- Journal of Chemical Information and Modeling, Vol. 51, Issue 8
Theoretical Insights into the Substitution Effect of Phenanthroline Derivatives on Am(III)/Eu(III) Separation
journal, February 2023
- Lei, Xia-Ping; Wu, Qun-Yan; Wang, Cong-Zhi
- Inorganic Chemistry, Vol. 62, Issue 6
Preorganization of diglycolamides on the calix[4]arene platform and its effect on the extraction of Am(III)/Eu(III)
journal, September 2012
- Iqbal, Mudassir; Mohapatra, Prasanta K.; Ansari, Seraj A.
- Tetrahedron, Vol. 68, Issue 38
On the Origin of Covalent Bonding in Heavy Actinides
journal, July 2017
- Kelley, Morgan P.; Su, Jing; Urban, Matthew
- Journal of the American Chemical Society, Vol. 139, Issue 29
Molecular Dynamics Studies of Concentrated Binary Aqueous Solutions of Lanthanide Salts: Structures and Exchange Dynamics
journal, January 2010
- Duvail, Magali; Ruas, Alexandre; Venault, Laurent
- Inorganic Chemistry, Vol. 49, Issue 2
Recent advances in computational modeling and simulations on the An(III)/Ln(III) separation process
journal, July 2012
- Lan, Jian-Hui; Shi, Wei-Qun; Yuan, Li-Yong
- Coordination Chemistry Reviews, Vol. 256, Issue 13-14
Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures
journal, December 2016
- Bogart, Justin A.; Cole, Bren E.; Boreen, Michael A.
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 52
VMD: Visual molecular dynamics
journal, February 1996
- Humphrey, William; Dalke, Andrew; Schulten, Klaus
- Journal of Molecular Graphics, Vol. 14, Issue 1