f‐block MOFs: A Pathway to Heterometallic Transuranics

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.

Synthetic Control of Thorium Metal‐Organic Frameworks for Sequencing and Sensing of Radioiodine Species

“…Unlocking the full potential of actinide‐bearing materials is essential in tackling the escalating issue of radioactive waste accumulation. [ 1‐4 ] However, obtaining a comprehensive understanding of their structures and physiochemical properties represents the crucial first step. [ 5‐9 ] Actinide‐bearing metal‐organic frameworks (An‐MOFs), which are constructed from actinide centers and organic linkers in a hierarchical manner, have attracted particular attention due to their extensive range of synthetically accessible and remarkable structures.…”

Assembling a Heterobimetallic Actinide Metal‐Organic Framework by a Reaction‐Induced Preorganization Strategy

“…Up to now, only one case applying the cluster extension approach successfully yields structurally well‐defined heterobimetallic An‐MOFs [3a] . Other efforts to this aim only yield mixed An‐MOFs where the spatial arrangement of metals is unclear [4b, 13] . The lack of unambiguous structure information of heterobimetallic An‐MOFs vastly hinders the exploration of their utilities and frustrates the further elucidation of structure–property relationship.…”