A Quasi-relativistic Density Functional Theory Study of the Actinyl(VI, V) (An = U, Np, Pu) Complexes with a Six-Membered Macrocycle Containing Pyrrole, Pyridine, and Furan Subunits

Actinyl­(VI, V) (An = U, Np and Pu) complexes of the recently reported hybrid macrocycle, cyclo[1]­furan[1]­pyridine[4]­pyrrole (denoted as H<sub>4</sub>L), have been studied using density functional theory in combination with the small-core scalar-relativistic effective core potentials and corresponding (14s13p10d8f6g)/[ 10s9p5d4f3g] basis sets in the segmented contraction scheme. On the basis of our calculations, the pyrrole nitrogen atoms that possess the shortest An-L bonds and strongest basicity are the main donor atoms that contribute to the formation of actinyl­(VI, V) complexes. The natural population analysis (NPA) suggests higher ligand-to-actinyl charge transfer in the actinyl­(VI) complexes than in their actinyl­(V) analogues, which account for the higher decomposition energies of the former. A significant actinide-to-ligand spin density delocalization in the uranyl­(V) and neptunyl­(V) complexes was observed owing to the redistribution of spin density caused by complexation. A thermodynamic analysis indicates that the formation of the actinyl­(VI, V) complexes are exothermic reactions in CH<sub>2</sub>Cl<sub>2</sub> solvent, where the uranyl cations show the highest selectivity. In aqueous solution containing chloride ions, for complexing with macrocycle H<sub>4</sub>L, the plutonyl­(VI) and uranyl­(V) cations possess the highest selectivity among actinyl­(VI) and (V) cations, respectively. This work can shed light on the design of macrocycle complexes for actinide recognition and extraction in the future.