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Comprehensive Summary: The second example of tetravalent plutonium carboxyl‐based organic framework, 242Pu(OH)[PO[(C6H4)COO]3]·H2O, 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 [Pu2O16]. 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 242Pu. This result enriches the inventory of tetravalent plutonium compounds and provides an insight into the irradiation resistance of metal‐organic frameworks. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: We reported the synthesis, single crystal structure, and solid‐state UV‐Vis‐NIR spectroscopy of a new transplutonium metal‐organic framework (MOFs), Am(H2O)[PO[(C6H4)COO]3], denoted as AmTPO (TPO = tris(4‐carboxylphenyl)‐phosphineoxide). AmTPO forms a three‐dimensional metal−organic framework structure with americium dimers as the secondary building unit. Clear 5f → 5f transitions attributed to trivalent americium was observed in the absorption spectrum of AmTPO ranging from 300 to 1200 nm. Notably, AmTPO can maintain the crystallinity with no observable structural degradation within several months after being synthesized, revealing a long‐term radiation resistance of this structure and the potential application of MOFs as a platform for nuclear waste disposal. [ABSTRACT FROM AUTHOR]