Plutonium and Cerium Perrhenate/Pertechnetate Coordination Polymers and Frameworks.

Spent nuclear fuel (SNF) contains transuranic and lanthanide species, which are sometimes recovered and repurposed. One particularly problematic fission product, 99 TcO 4 - , hampers this recovery via coextraction with high valence metals, perhaps by complexation during aqueous reprocessing of SNF. There is limited molecular-level knowledge concerning the coordination chemistry between TcO 4 - or its well-known surrogate ReO 4 - and transuranic/lanthanide species. In the current study, we investigated the coordination of ReO 4 - /TcO 4 - with plutonium and cerium cations by structural and chemical characterization of a series of isolated extended solids. In this study, Ce represents both trivalent lanthanides and is considered a surrogate for Pu, respectively, in its common trivalent and tetravalent oxidation states. The structural elucidation of the seven isolated crystalline solids revealed that ReO 4 - /TcO 4 - directly connects to Pu IV , Pu VI O 2 2+ , Ce III , and Ce IV in the terminal and bridging coordination modes, leading to 1-, 2-, and 3-dimensional frameworks. For example, ReO 4 - coordination to Pu(IV) formed a 1D chain or 2D framework, isostructural with previously isolated Th(IV) compounds. However, Pu VI O 2 2+ alternating with ReO 4 - led to a unique 1D chain, different from the prior-reported U(VI)/Np(VI)-ReO 4 - /TcO 4 - structures. Coordination of ReO 4 - /TcO 4 - with Ce(III) promotes the assembly of 3D frameworks. Finally, attempted synthesis of a Ce(IV)-ReO 4 - compound resulted in a 2D framework with a mixed-valence Ce III/IV . The highly acidic reaction conditions supported the reduction of both Ce IV and Tc VII , challenging isolation of compounds featuring these species. Only one TcO 4 -containing structure was obtained in this study (Ce III -TcO 4 3D framework), vs the six total Ce/Pu-ReO 4 compounds. Our three Pu-ReO 4 crystal structures are the first reported and translated to atomic-level information about Pu-TcO 4 coordination in nuclear fuel reprocessing scenarios, in addition to broadening our knowledge of bonding trends in the early, high-valence actinides.