title: 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.
abstract: 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 UO 6 and UO 7 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.
authors.affiliation: Department of Chemistry and Biochemistry and Center for Actinide Science, Auburn University, Auburn, Alabama 36849, USA.
authors.forename: Anna-Gay D
authors.initials: AG
authors.lastname: Nelson
authors.forename: Travis H
authors.initials: TH
authors.lastname: Bray
authors.forename: Wei
authors.initials: W
authors.lastname: Zhan
authors.forename: Richard G
authors.initials: RG
authors.lastname: Haire
authors.forename: Todd S
authors.initials: TS
authors.lastname: Sayler
authors.forename: Thomas E
authors.initials: TE
authors.lastname: Albrecht-Schmitt