Insights into the Complexation of Actinides by Diethylenetriaminepentaacetic Acid from Characterization of the Americium(III) Complex

Diethylenetriaminepentaacetic acid (DTPA) is a frequently used chelator in the nuclear and medical industries, especially for the complexation of trivalent actinides. However, structural data on these complexes in the solid-state have long remained elusive. Herein, a detailed structural analysis of the presented crystal structures of [C(NH₂)₃]₄[Nd(DTPA)]₂·<em>n</em>H₂O and [C(NH₂)₃]₄[Am(DTPA)]₂·<em>n</em>H₂O, where [C(NH₂)₃]⁺ is guanidinium, details the subtle differences in the Lewis acidity between a lanthanide/actinide pair of similar ionic sizes. Contractions in nitrogen–metal bond lengths between neodymium(III) and americium(III) were observed, while the metal–oxygen bonds remained relatively consistent, highlighting the marginal favorability for actinide complexation over the lanthanides with moderately soft N-donors. Spectroscopic analysis shows significant splitting of many transitions and relatively strong electronic interactions with traditionally low-intensity transitions in the americium complex, as is demonstrated in the ⁷F₀→⁷F₅ transitions. Pressure-induced spectroscopic analysis showed surprisingly little effect on the americium complex, with 5<em>f</em>→5<em>f</em> transitions either not shifting or marginally shifting from 2 to 3 nm at 11.93 ± 0.06 GPa─atypical of a soft, N-donor americium complex under pressure. Finally, large voids occupied by water molecules in between the complexes within the crystal structure may be responsible for the lack of pressure response in the 5<em>f</em>→5<em>f</em> transitions.. Authors: Rotermund, Brian M. [Colorado School of Mines, Golden, CO (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)] (ORCID:0000000223790119); Beck, Nicholas B. [Colorado School of Mines, Golden, CO (United States)] (ORCID:000000015687192X); Wineinger, Hannah B. [Colorado School of Mines, Golden, CO (United States)] (ORCID:000000034070999X); Sperling, Joseph M. [Colorado School of Mines, Golden, CO (United States)] (ORCID:0000000319165633); Horne, Gregory P. [Idaho National Laboratory (INL), Idaho Falls, ID (United States)] (ORCID:0000000305960660). DOE Contract: SC0024191. Subjects: absorption spectroscopy; actinides; crystal structure; guanidine; ions