A Tetravalent Plutonium Organic Framework Containing [ Pu 2 O 16 ] Dimers as Secondary Building Units: Synthesis, Structure, and Radiation Stability

作者：Yugang Zhang, Yingzhe Du, Lili Li, Tao Ye, Kai Li, Hailong Zhang, Yanlong Wang, Lanhua Chen, Yaxing Wang, Zhifang Chai, Shuao Wang · 发表于：Chinese Journal of Chemistry · 年份：2023 · DOI：10.1002/cjoc.202200833 · 被引用次数：8 · 研究领域：Radioactive element chemistry and processing、Metal-Organic Frameworks: Synthesis and Applications、Covalent Organic Framework Applications

Comprehensive Summary The second example of tetravalent plutonium carboxyl‐based organic framework, 242 Pu(OH)[PO[(C 6 H 4 )COO] 3 ]·H 2 O, termed as PuTPO (TPO = tris(4‐carboxylphenyl)‐phosphineoxide), was reported in this work. A series of characterizations of PuTPO, such as X‐ray crystallography and solid‐state UV‐Vis‐NIR spectroscopy, were carried out to expatiate its structure and physicochemical properties. PuTPO is constructed by dimers of the plutonium‐oxygen subunit of [Pu 2 O 16 ]. Characteristic peaks located at approximately 1100 nm can be considered to be the fingerprint peaks of tetravalent plutonium. While PuTPO can maintain high crystallinity within several months after synthesis, it exhibits a radiation‐induced swelling effect probed by the expansion of cell parameter of b axis after self‐irradiation from α‐decay of 242 Pu. This result enriches the inventory of tetravalent plutonium compounds and provides an insight into the irradiation resistance of metal‐organic frameworks.