Elucidating Actinide-Pertechnetate and Actinide-Perrhenate Bonding via a Family of Th-TcO 4 and Th-ReO 4 Frameworks and Solutions.

Technetium-99, a β-emitter produced from 235 U fission, poses a challenge for the nuclear industry due to co-extraction of pertechnetate (TcO 4 - ) with the actinides (An) during nuclear fuel reprocessing. Previous studies suggested that direct coordination of pertechnetate with An plays an important role in the coextraction process. However, few studies have provided direct evidence for An-TcO 4 - bonding in the solid state, and even fewer in solution. The present study describes synthesis and structural elucidation of a family of thorium(IV)-pertechnetate/perrhenate (ReO 4 - , nonradioactive surrogate) compounds, which is obtained by dissolution of thorium oxyhydroxide in perrhenic/pertechnic acid followed by crystallization, with or without heating. For reaction ratios of 3:1, 4:1, and 6:1 MO 4 - /Th(IV) (M = Tc, Re), the crystallized compounds reflect the same ratio, suggesting facile and flexible coordination. Nine structures reveal 1-dimensional and 2-dimensional frameworks with varying topologies. While a multitude of compounds isolated from 4:1 (and 6:1) reaction solutions feature Th monomers linked by MO 4 - , the 3:1 reaction solution yielded the well-known dihydroxide-bridged thorium dimer, linked, and capped by MO 4 - . Density functional theory calculations on ReO 4 - /TcO 4 - isomorphs suggest similar bonding characteristics in the solid state, but experimental solution characterization noted differences. Specifically, small-angle X-ray scattering studies suggest the bonding of Th-TcO 4 - persists in solution, while Th-ReO 4 - bonding is less apparent.