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The preorganized tetradentate 2,9-diamido-1,10-phenanthroline ligand with hard-soft donors combined in the same molecule has been found to possess high selectivity toward actinides in an acidic aqueous solution. In this work, density functional theory (DFT) coupled with the quasi-relativistic small-core pseudopotential method was used to investigate the structures, bonding nature, and thermodynamic behavior of uranium(VI), neptunium(V), and plutonium(IV,VI) with phenanthrolineamides. Theoretical optimization shows that Et-Tol-DAPhen and Et-Et-DAPhen ligands are both coordinated with actinides in a tetradentate chelating mode through two N donors of the phenanthroline moiety and two O donors of the amide moieties. It is found that [AnO2L(NO3)](n+) (An = U(VI), Np(V), Pu(VI); n = 0, 1) and PuL(NO3)4 are the main 1:1 complexes. With respect to 1:2 complexes, the reaction [Pu(H2O)9](4+)(aq) + 2L(org) + 2NO3(-)(aq) → [PuL2(NO3)2](2+)(org) + 9H2O(aq) might be another probable extraction mechanism for Pu(IV). From the viewpoint of energy, the phenanthrolineamides extract actinides in the order of Pu(IV) > U(VI) > Pu(VI) > Np(V), which agrees well with the experimental results. Additionally, all of the thermodynamic reactions are more energetically favorable for the Et-Tol-DAPhen ligand than the Et-Et-DAPhen ligand, indicating that substitution of one ethyl group with one tolyl group can enhance the complexation abilities toward actinide cations (anomalous aryl strengthening).

A series of actinide (An) species of L-An-N compounds [An = Pa-Pu, L = [N(CH2CH2NSiPr(i)3)3](3-), Pr(i) = CH(CH3)2] have been investigated using scalar relativistic density functional theory (DFT) without considering spin-orbit coupling effects. The ground state geometric and electronic structures and natural bond orbital (NBO) analysis of actinide compounds were studied systematically in neutral and anionic forms. It was found that with increasing actinide atomic number, the bond length of terminal multiple An-N1 bond decreases, in accordance with the actinide contraction. The Mayer bond order of An-N1 decreases gradually from An = Pa to Pu, which indicates a decrease in bond strength. The terminal multiple bond for L-An-N compounds contains one σ and two π molecular orbitals, and the contributions of the 6d orbital to covalency are larger in magnitude than the 5f orbital based on NBO analysis and topological analysis of electron density. This work may help in understanding of the bonding nature of An-N multiple bonds and elucidating the trends and electronic structure changes across the actinide series. It can also shed light on the construction of novel An-N multiple bonds.

In this work, we reported a phenanthroline-based tetradentate ligand with hard-soft donors combined in the same molecule, N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV-vis spectrometry. Density functional theory (DFT) calculations reveal that the An-N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu-N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward actinides. This ligand possesses merits of both alkylamide and 2,9-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient actinide extraction and the selectivity toward minor actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning.