Park Kyoung Chul, Kittikhunnatham Preecha, Lim Jaewoong, Thaggard Grace C, Liu Yuan, Martin Corey R, Leith Gabrielle A, Toler Donald J, Ta An T, Birkner Nancy, Lehman-Andino Ingrid, Hernandez-Jimenez Alejandra, Morrison Gregory, Amoroso Jake W, Zur Loye Hans-Conrad, DiPrete Dave P, Smith Mark D, Brinkman Kyle S, Phillpot Simon R, Shustova Natalia B
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA.
Department of Chemistry, Chulalongkorn University, Bangkok, 10330, Thailand.
Angew Chem Int Ed Engl. 2023 Jan 26;62(5):e202216349. doi: 10.1002/anie.202216349. Epub 2022 Dec 19.
A novel series of heterometallic f-block-frameworks including the first examples of transuranic heterometallic U/ Pu-metal-organic frameworks (MOFs) and a novel monometallic 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.
报道了一系列新型的异金属f-块框架，包括首例超铀异金属U/Pu金属有机框架（MOF）以及一种新型的单金属Pu类似物。结合理论计算，我们探究了异金属锕系元素（An）-MOF形成的动力学和热力学，并报道了U到Th的金属转移速率的首个值。我们得出结论，铀酰物种的形成可能是固态复分解反应的驱动力。研究了费米边缘附近的态密度、生成焓、带隙、质子亲和能以及热/化学稳定性与金属比例的关系。此外，我们实现了An整合理论最大容量的97%。这些研究揭示了锕系元素化学的基本方面，也为包括放射性同位素热电发电机或金属放射性药物在内的新型含An材料的开发指明了方向。
