Advancement of Actinide Metal–Organic Framework Chemistry via Synthesis of Pu-UiO-66

We report the synthesis
and characterization of the first plutonium
metal–organic framework (MOF). Pu-UiO-66 expands the established
UiO-66 series, which includes transition metal, lanthanide, and early
actinide elements in the hexanuclear nodes. The thermal stability
and porosity of Pu-UiO-66 were experimentally determined, and multifaceted
computational methods were used to corroborate experimental values,
examine inherent defects in the framework, decipher spectroscopic
signatures, and elucidate the electronic structure. The crystallization
of a plutonium chain side product provides direct evidence of the
competition that occurs between modulator and linker in MOF syntheses.
Ultimately, the synthesis of Pu-UiO-66 demonstrates adept control
of Pu­(IV) coordination under hydrolysis-prone conditions, provides
an opportunity to extend trends across isostructural UiO-66 frameworks,
and serves as the foundation for future plutonium MOF chemistry.