Neptunium exhibits rich redox and coordination chemistry, that is relatively unexplored due to its radioactivity and limited supplies. A thorough understanding of neptunium chemistry is essential for discernment of the 5<i>f</i> electron contribution to bonding and developing appropriate techniques for nuclear waste stewardship. The prevalence of pentavalent neptunium promotes rare bonding motifs called actinyl-actinyl interactions (AAIs) that result in unique connectivity patterns. We explore the coordination chemistry of neptunium using metal–organic frameworks (MOFs) to understand interactions between neptunium and organic species. Here we report a neptunium MOF structure consisting of anionic neptunyl sheets dominated by AAIs, bridged by 1,4-napthalene dicarboxylic acid. Using X-ray diffraction, Raman spectroscopy, infra-red spectroscopy, and thermal gravimetric analysis, we examine the bonding patterns and properties of the structure gain a better understanding of fundamental neptunium (V) chemistry.

Exploration of neptunium(V) chemistry via synthesis of metal–organic frameworks

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ACS Fall 2022

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