Americium Oxalate: An Experimental and Computational Investigation of Metal–Ligand Bonding

Arteaga, Ana L.; Nicholas, Aaron D.; Ducati, Lucas C.; Autschbach, Jochen; Surbella, Robert G.

doi:10.1021/acs.inorgchem.2c03976

Title: Americium Oxalate: An Experimental and Computational Investigation of Metal–Ligand Bonding

Journal Article · Wed Mar 15 00:00:00 EDT 2023 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.2c03976· OSTI ID:1968457

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Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Sao Paulo (Brazil)
State Univ. of New York (SUNY), Buffalo, NY (United States)

A novel actinide-containing coordination polymer, [Am(C₂O₄)(H₂O)₃Cl] (Am-1), has been synthesized and structurally characterized. The crystallographic analysis reveals that the structure is two-dimensional and comprised of pseudo-dimeric Am³⁺ nodes that are bridged by oxalate ligands to form sheets. Each metal center is nine-coordinate, forming a distorted capped square antiprism geometry with a C₁ symmetry, and features bound oxalate, aqua, and chloro ligands. The Am³⁺–ligand bonds were probed computationally using the quantum theory of atoms in molecules nd natural localized molecular orbital approaches to investigate the underlying mechanisms and hybrid atomic orbital contributions therein. The analyses indicate that the bonds within Am-1 are predominantly ionic and the 5f shell of the Am³⁺ metal centers does not add a significant covalent contribution to the bonds. Further, our bonding assessment is supported by measurements on the optical properties of Am-1 using diffuse reflectance and photoluminescence spectroscopies. The position of the principal absorption band at 507 nm (⁵L_6' ← ⁷F_0') is notable because it is consistent with previously reported americium oxalate complexes in solution, indicating similarities in the electronic structure and ionic bonding. Compound Am-1 is an active phosphor, featuring strong bright-blue oxalate-based luminescence with no evidence of metal-centered emission.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; São Paulo Research Foundation (FAPESP)

Grant/Contract Number:: AC05-76RL01830; FWP 73200; SC0001136; 2017/17750-3; 306844/2020-6

OSTI ID:: 1968457

Report Number(s):: PNNL-SA-179534

Journal Information:: Inorganic Chemistry, Vol. 62, Issue 12; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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