Role of O Substitution in Expanded Porphyrins on Uranyl Complexation: Orbital- and Density-Based Analyses

Search for new U(VI) sequestering macrocyclic ligands is an important area of research due to manifold applications. Besides hard- or soft-donor-based ligands, mixed-donor ligands are also gaining popularity in achieving optimized performances. However, how the combination of hard-soft-donor centers alters the bonding interactions with U(VI) is still not well-understood. Moreover, a consensus is yet to be reached on the nature and role of underlying covalent interactions in mixed N,O-donor ligands. In this work, using the relativistic density functional theory (DFT), we attempted to address these intriguing issues by investigating the subtle change in bonding characteristics of the uranyl ion upon binding with an expanded porphyrin, viz. sapphyrin, with subsequent O substitutions at the cavity. The results obtained from a range of modern analysis tools suggest that in the O-substituted sapphyrin variants, UO₂²⁺ prefers to bind with N over O, and an increase in the number of O-donor sites at the cavity prompts UO₂²⁺ to have a better interaction with the rest of the N-donor-centers. Although O donors are involved in more numbers of mixed molecular orbitals, the variation in the amplitude of overlap and the better σ-donation ability favor N to have stronger bonding interactions with uranyl. Molecular orbital (MO) and density of states (DOS) analyses show favorable participation of U(d), and the involvement of U(f) orbitals in bonding is of a low extent but non-negligible. Although electrostatic interaction dominates at U-O/N bonds in the equatorial plane, the quantum theory of atoms in molecules descriptors, MO analysis, and overlap-integral calculations confirm the presence of underlying near-degeneracy-driven covalent interactions.