f-block MOFs: A Pathway to Heterometallic Transuranics

Kyoung Chul Park; Preecha Kittikhunnatham; Jaewoong Lim; Grace C Thaggard; Yuan Liu; Corey R Martin; Gabrielle A Leith; Donald J Toler; An T Ta; Nancy Birkner; Ingrid Lehman-Andino; Alejandra Hernandez-Jimenez; Gregory Morrison; Jake W Amoroso; Hans-Conrad Zur Loye; Dave P DiPrete; Mark D Smith; Kyle S Brinkman; Simon R Phillpot; Natalia B Shustova

doi:10.1002/anie.202216349

f-block MOFs: A Pathway to Heterometallic Transuranics

Angew Chem Int Ed Engl. 2023 Jan 26;62(5):e202216349. doi: 10.1002/anie.202216349. Epub 2022 Dec 19.

Authors

Kyoung Chul Park¹, Preecha Kittikhunnatham², Jaewoong Lim¹, Grace C Thaggard¹, Yuan Liu³, Corey R Martin⁴, Gabrielle A Leith¹, Donald J Toler¹, An T Ta³, Nancy Birkner^{5

6}, Ingrid Lehman-Andino⁴, Alejandra Hernandez-Jimenez⁴, Gregory Morrison¹, Jake W Amoroso⁴, Hans-Conrad Zur Loye^{1

4}, Dave P DiPrete⁴, Mark D Smith¹, Kyle S Brinkman^{5

6}, Simon R Phillpot³, Natalia B Shustova¹

Affiliations

¹ Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA.
² Department of Chemistry, Chulalongkorn University, Bangkok, 10330, Thailand.
³ Department of Materials Science and Engineering, University of Florida, Gainesville, FL 32611, USA.
⁴ Savannah River National Laboratory, Aiken, SC 29808, USA.
⁵ Department of Materials Science and Engineering, Clemson University, Clemson, SC 29634, USA.
⁶ Center for Nuclear Environmental Engineering Sciences and Radioactive Waste Management (NEESRWM), Clemson University, Clemson, SC 29634, USA.

PMID: 36450099
DOI: 10.1002/anie.202216349

Abstract

A novel series of heterometallic f-block-frameworks including the first examples of transuranic heterometallic ²³⁸ U/²³⁹ Pu-metal-organic frameworks (MOFs) and a novel monometallic ²³⁹ Pu-analog are reported. In combination with theoretical calculations, we probed the kinetics and thermodynamics of heterometallic actinide(An)-MOF formation and reported the first value of a U-to-Th transmetallation rate. We concluded that formation of uranyl species could be a driving force for solid-state metathesis. Density of states near the Fermi edge, enthalpy of formation, band gap, proton affinity, and thermal/chemical stability were probed as a function of metal ratios. Furthermore, we achieved 97 % of the theoretical maximum capacity for An-integration. These studies shed light on fundamental aspects of actinide chemistry and also foreshadow avenues for the development of emerging classes of An-containing materials, including radioisotope thermoelectric generators or metalloradiopharmaceuticals.

Keywords: Actinides; Heterometallic; Metal-Organic Frameworks; Plutonium; Transmetallation.

Abstract

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