Gas-Phase Actinyl Chemistry of N-Heterocyclic Ligands: A Joint Theoretical and Experimental Study

摘要

As the largest domestic source of low-carbon electricity, nuclear energy production is instrumental to meet increasing demand while limiting greenhouse gas emissions. The actinide chemistry of ligands with soft N-and S-donor atoms has experienced strong development during the last decade, and the topic is becoming the focus of research from the perspective of tackling the challenging separation of transuranic actinides in the nuclear fuel cycle. A better molecular-level understanding of the coordination and chemistry of these ligands containing multiple bindings sites to actinyl ions will pave the way to designing new ligands with improved selectivity. In current work, we focus on the coordination chemistry of actinyl ions with ligands composed of multiple competitive binding sites, including nitrogen, sulfur, and oxygen chelating groups. Due to the complexity of the solution systems, we employ a joint effort combining first-principle methods and gas-phase collision-induced dissociation experiments to unravel the nature of chemical bonding in f-element/ligand complexes, and bond activation induced by actinide centers.