Department of Civil & Environmental Engineering & Earth Sciences, University of Notre Dame, 301 Stinson-Remick, Notre Dame, Indiana 46556, United States.
Department of Chemistry, Chemical Theory Center and Minnesota Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455, United States.
J Am Chem Soc. 2020 May 20;142(20):9363-9371. doi: 10.1021/jacs.0c01895. Epub 2020 May 7.
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.
我们报告了首例钚金属有机骨架（MOF）的合成与表征。Pu-UiO-66 扩展了已确立的 UiO-66 系列，其中包含了六核节点中的过渡金属、镧系元素和早期锕系元素。Pu-UiO-66 的热稳定性和孔隙率通过实验确定，并采用多种计算方法来佐证实验值，研究结构中的固有缺陷，解析光谱特征，并阐明电子结构。钚链副产物的结晶为 MOF 合成中调节剂和配体之间发生竞争提供了直接证据。最终，Pu-UiO-66 的合成展示了在水解倾向条件下对 Pu(IV)配位的熟练控制，为在同构 UiO-66 骨架中扩展趋势提供了机会，并为未来的钚 MOF 化学奠定了基础。
