The f-elements have attracted increasing attention due to their particular properties and implications in different fields such as biomedicine or energy technology. Unraveling the chemistry of Lanthanide and Actinides and in particular Transplutonium elements requires theoretical and experimental approaches. Synthetic chemists have devoted tremendous efforts to design and synthesize improved metal binding units and chelating platforms for the f-elements. Inspired by naturally occurring siderophores, polydentate ligands based on 1,2-hydroxypyridinone (HOPO) units have shown remarkable affinity for f-block metals and outstanding spectroscopic features of the resulting complexes. In this work, we have rationally designed a new macrocylic ligand functionalized with HOPO units that forms highly thermodynamically stable complexes with f-elements. The energy of the triplet excited states of the ligand and the rigid macrocyclic backbone allow effective sensitization and subsequent radiative decay of Lanthanides i.e. Sm (III), Eu (III), Tb (III), and Dy (III) and Actinides i.e. Cm (III) and Bk (IV) complexes. We performed luminescence experiments to determine coordination properties and molecular structure in solution. Interestingly, time dependent luminescence data indicate the presence of a water molecule in the first coordination sphere of the metal ion. To confirm our hypothesis of a hydrated complex, we performed X-ray absorption spectroscopy, which corroborates our initial findings. Despite the presence of a water molecule, the conditional stability constants are up to two orders of magnitude higher than that of the benchmark DTPA, the FDA-approved heavy element decontamination agent. In addition, the presence of an exchangeable water molecule makes this new HOPO derivative ligand a great candidate for Gd-based MRI contrast agents.

1,2-Hydroxypyridinonate derivatives of macrocyclic ligands: Towards new chelators for Lanthanide and Actinide ions

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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