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.