Further Examples of the Failure of Surrogates to Properly Model the Structural and Hydrothermal Chemistry of Transuranium Elements: Insights Provided by Uranium and Neptunium Diphosphonates

In situ hydrothermal reduction of Np(VI) to Np(IV) in the presence of methylenediphosphonic acid (C1P2) results in the crystallization of Np[CH2(PO3)2](H2O)2 (NpC1P2−1). Similar reactions have been explored with U(VI) resulting in the isolation of the U(IV) diphosphonate U[CH2(PO3)2](H2O) (UC1P2−1), and the two U(VI) diphosphonates (UO2)2[CH2(PO3)2](H2O)3·H2O (UC1P2−2) and UO2[CH2(PO3H)2](H2O) (UC1P2−3). Single crystal diffraction studies of NpC1P2−1 reveal that it consists of eight-coordinate Np(IV) bound by diphosphonate anions and two coordinating water molecules to create a polar three-dimensional framework structure wherein the water molecules reside in channels. The structure of UC1P2−1 is similar to that of NpC1P2−1 in that it also adopts a three-dimensional structure. However, the U(IV) centers are seven-coordinate with only a single bound water molecule. UC1P2−2 and UC1P2−3 both contain U(VI). Nevertheless, their structures are quite distinct with UC1P2−2 being composed of corrugated layers containing UO6 and UO7 units bridged by C1P2; whereas, UC1P2−3 is found as a polar three-dimensional network structure containing only pentagonal bipyramidal U(VI). Fluorescence measurements on UC1P2−2 and UC1P2−3 exhibit emission from the uranyl moieties with classical vibronic fine-structure.