Uranyl-Tc(vii)/Tc(v) hybrid clusters

Abstract

Pertechnetate (⁹⁹Tc^VIIO₄⁻), reduced Tc, and actinides co-exist in spent nuclear fuel and legacy wastes. They co-transport in fuel reprocessing and waste disposal scenarios, necessitating an understanding of co-speciation. Here, we report five new molecular cluster/framework structures with pentameric and tetrameric uranyl building units decorated by TcO₄⁻/ReO₄⁻ oxoanions, or fused with the reduced technetyl cation Tc(V)O. The latter, obtained by Tc auto-reduction (without the intentional introduction of a reducing environment), broadens the basis for Tc-reduction and the burgeoning polyoxometalate-like behavior of technetium.