Changes in nitrate binding with lanthanides in BLPhen complexes

Reddy, Th. Dhileep N.; Ivanov, Alexander S.; Driscoll, Darren M.; Jansone-Popova, Santa; Jiang, De-en

doi:10.1016/j.molliq.2023.122573

Changes in nitrate binding with lanthanides in BLPhen complexes

Journal Article · Tue Jul 11 00:00:00 EDT 2023 · Journal of Molecular Liquids

DOI:https://doi.org/10.1016/j.molliq.2023.122573· OSTI ID:1995657

Reddy, Th. Dhileep N. ^[1]; ^[2]; ^[2]; Jansone-Popova, Santa ^[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)

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.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1995657

Journal Information:: Journal of Molecular Liquids, Journal Name: Journal of Molecular Liquids Vol. 387; ISSN 0167-7322

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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