Impact of Ligand Structures on Precipitation Reactions of Uranyl Nitrate Coordination Polymers with Diamide/Dicarbamide Cross-Linkers.

In relevance to advanced nuclear fuel recycling, we investigated the structural chemistry of UO2(NO3)2 coordination polymers bearing trans-1,4-cyclohexanediamine-based cyclic/acyclic diamides/dicarbamide cross-linkers (L1-L6) to know how the ligand structure impacts precipitation behavior of UO2 2+ from HNO3(aq). In a similar manner to the γ-lactam analogue (L2) we reported previously, 1D coordination polymers of [UO2(NO3)2(Lx)] n were obtained in the use of any Lx's having β-/δ-lactam (L1, L3), acetamide (L4), propionamide (L5), and N,N,N'-trimethylcarbamide (L6) terminals. These compounds exhibit the typical structural features of uranyl nitrates. Indeed, [UO2(NO3)2(Lx)] n (x = 2-6) deposited in 71-90% yield from 3 M HNO3(aq). In contrast, no [UO2(NO3)2(L1)] n precipitated under the same condition. The packing efficiency of [UO2(NO3)2(Lx)] n and the electronic nature of Lx seem to control the solubility of [UO2(NO3)2(Lx)] n . Reaction kinetics of precipitation of [UO2(NO3)2(Lx)] n with the cyclic diamides (L2 and L3) was faster than that of the acyclic diamides (L4 and L5), being associated with the rotational isomerism around the amide C-N bonds occurring only in the latter series. Despite the availability of similar E-Z isomerism, the precipitation kinetics in the use of dicarbamide L6 was as rapid as the cyclic amides (L2, L3), being ascribed to the lower energy barrier in its C-N bond rotation compared with those in the acyclic diamides (L4, L5).