Atomistic Insights into Structure and Dynamics of Neodymium(III) Complexation with a Bis-lactam Phenanthroline Ligand in the Organic Phase

[Image: see text] 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(3))(3) in the DCE solvent. BLPhen can bind to Nd(III) in either 1:1 or 2:1 fashion. In the 1:1 complex, three nitrates bind to Nd(III) via the bidentate mode in the first solvation shell, leading to the formation of a neutral complex, [Nd(BLPhen)(NO(3))(3)](0), in the organic phase. In contrast, there are two nitrates in the first solvation shell in the 2:1 complex, creating a charged complex, [Nd(BLPhen)(2)(NO(3))(2)](+). The third nitrate was found to be far away from the metal center, migrating to the outer solvation shell. Our simulations show that the binding pocket formed by the two rigid BLPhen ligands allows ample space for two nitrates to bind to the Nd(III) center from opposite sides. Our findings of two nitrates in the first solvation shell of the 2:1 complex and the corresponding bond distances agree well with the available crystal structure. This study represents the first accurate FPMD modeling of the BLPhen–Nd(III) complexes in an explicit organic solvent and opens the door to more atomistic understanding of REE separations from first principles.