Understanding the Interaction of Uranyl Cation with Two C-Pivot Tripodal Amides: Synthesis, Complexation, Microcalorimetry, and DFT Studies

Complexation of uranyl ions with two structurally related C-pivotal tripodal amides with varying spacer lengths, synthesized for the first time, was studied by optical spectroscopy. In the tripodal amides, the coordination was through the carbonyl O atoms where the carbonyl groups were away from the central C-atom by three spacer atoms (L_I) and four spacer atoms (L_II), respectively. Increasing the spacer atoms going from L_I to L_II favors the complexation with the linear uranyl cations and results in stronger complex formation. The complexation heat between the uranyl cations and the two amide ligands was directly measured by microcalorimetric titrations. The complexation with both the ligands was driven by exothermic enthalpy and positive entropy changes. Formation of the complex proceeded by the replacement of water molecules from the primary coordination sphere of the uranyl cation. Both ligands formed bisolvated (ML₂-type) complexes in which one unit of the ligand binds in a monodentate manner and the other in a bidentate mode. Density functional theory calculations further supported our experimental observations.