Abstract

Pertechnetate (99TcVIIO4-), 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.

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