Controlling the Reduction of Chelated Uranyl to Stable Tetravalent Uranium Coordination Complexes in Aqueous Solution

The solution-state interactions between octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) chelating ligands and uranium were investigated and characterized by UV-visible spectrophotometry and X-ray absorption spectroscopy (XAS), as well as electrochemically via spectroelectrochemistry (SEC) and cyclic voltammetry (CV) measurements. Depending on the selected chelator, we demonstrate the controlled ability to bind and stabilize U^IV, generating with 3,4,3-LI(1,2-HOPO), a tetravalent uranium complex that is practically inert toward oxidation or hydrolysis in acidic, aqueous solution. At physiological pH values, we are also able to bind and stabilize U^IV to a lesser extent, as evidenced by the mix of U^IV and U^VI complexes observed via XAS. CV and SEC measurements confirmed that the U^IV complex formed with 3,4,3-LI(1,2-HOPO) is redox inert in acidic media, and U^VI ions can be reduced, likely proceeding via a two-electron reduction process.