Abstract
Abstract
Abstract We report the synthesis and evaluation of two CHON-compliant 4,7-dimethoxy-1,10-phenanthroline-2,9-dicarboxamide (DADOMePhen) ligands: an aromatic variant, Et-Tol-DADOMePhen (1), and an aliphatic analogue, TCH-DADOMePhen (2). Solvent extraction under SANEX conditions shows that ligand 1 has good Am/Eu selectivity in an optimal window of 0.1–0.5 M HNO3, achieving a maximum SFAm/Eu of 108.2 at 0.5 M HNO3, the highest reported for a lipophilic ligand of pure DAPhen-type molecular architecture to date. This performance inverts conventional acidity dependence: electron-donating methoxy substituents enhance metal–ligand covalency at low acidity but make the ligand susceptible to protonation at higher concentrations. Coordination and fluorescence studies indicate a 1:2 metal-to-ligand stoichiometry; single-crystal diffraction reveals the structure of ligand 1. Quantum-chemical calculations establish that methoxy groups tune electrostatic potential and frontier orbitals, strengthening bonding relative to parent Et-Tol-DAPhen. Beyond Am/Eu partitioning, ligand 1 may enable actinide/neptunium separations: at 0.1 M HNO3, calculated SFAm/Np, SFPu/Np, SFU/Np, and SFTh/Np reach 436, 1690, 9766, and 1953, respectively, reflecting mismatch between the dioxo Np(V) monocation and the ligand. This work establishes 4,7-methoxy derivatization as a design strategy to tune DAPhen-based extractant selectivity and introduces a ligand that could be useful for specialized low-acidity actinide/neptunium or lanthanide separations.
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@article{Zhang2026Tuned,
title = {Tuned 4,7-Methoxy-Derivatized DAPhen Ligands with Enhanced Selectivity for Am/Eu and An/Np Separations},
author = {Shi Lin Zhang and Lu Yu and Yong Qiang Wan and Yangyang Zhang and Huai Xin Hao and Zhi Peng Wang and John F. Gallagher and Jun Li and Pavle Mocilac},
journal = {Inorganic Chemistry},
year = {2026},
doi = {10.1021/acs.inorgchem.6c03342},
url = {https://doi.org/10.1021/acs.inorgchem.6c03342}
}
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