Journal of Physical Chemistry A, Vol.125, No.4, 920-932, 2021
Computational Study of Actinyl Ion Complexation with Dipyriamethyrin Macrocyclic Ligands
Relativistic density functional theory has been employed to characterize [AnO(2)(L)](0/-1) complexes, where An = U, Np, Pu, and Am, and L is the recently reported hexa-aza porphyrin analogue, termed dipyriamethyrin, which contains six nitrogen donor atoms (four pyrrolic and two pyridine rings). Shorter axial (An=O) and longer equatorial (An-N) bond lengths are observed when going from An(VI) to An(V). The actinide to pyrrole nitrogen bonds are shorter as compared to the bonds to the pyridine nitrogens; the former also play a dominant role in the formation of the actinyl (VI and V) complexes. Natural population analysis shows that the pyrrole nitrogen atoms in all the complexes carry higher negative charges than the pyridine nitrogens. Upon binding actinyl ions with the ligand a significant ligand-to-metal charge transfer takes place in all the actinyl (VI and V) complexes. The formation energy of the actinyl(VI,V) complexes in the gas-phase is found to decrease in the order of UO2L > PuO2L > NpO2 L > AmO2 L. This trend is consistent with results for the formation of complexes in dichloromethane solution. The calculated Delta G and Delta H values are negative for all the complexes. Energy decomposition analysis (EDA) indicates that the interactions between actinyl(V/VI) and ligand are mainly controlled by electrostatic components over covalent orbital interactions, and the covalent character gradually decreases from U to Am for both pentavalent and hexavalent actinyl complexes.