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

Rotermund, Brian M.; Beck, Nicholas B.; Wineinger, Hannah B.; Sperling, Joseph M.; Horne, Gregory P.; Brannon, Jacob P.; Greer, Rosalie; Albrecht, Thomas E.

doi:10.1021/acs.inorgchem.4c05386

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

Journal Article · Mon Mar 10 00:00:00 EDT 2025 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.4c05386· OSTI ID:3012123

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Colorado School of Mines, Golden, CO (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Colorado School of Mines, Golden, CO (United States)
Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Savannah River National Laboratory (SRNL), Aiken, SC (United States)

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·nH₂O and [C(NH₂)₃]₄[Am(DTPA)]₂·nH₂O, 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 5f→5f 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 5f→5f transitions.

View Accepted Manuscript (DOE)

Research Organization:: Colorado School of Mines, Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0024191

OSTI ID:: 3012123

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 11 Vol. 64; ISSN 0020-1669; ISSN 1520-510X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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