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.
Bibliographical noteFunding Information:
This material is based upon work supported by the Department of Energy, National Nuclear Security Administration, under Award no. DE-NA0003763 and the Arthur J. Schmitt Leadership Fellowship (A.M.H.). We thank the assistance of Dr. Allen Oliver for his crystallographic expertise, Dr. Zhijie Chen, Dr. Timur Islamoglu, and Dr. Xuan Zhang for their MOF characterization advice, and Dr. Ginger Sigmon and Jennifer Szymanowski for their time and experience.
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