Elucidating Self-Assembly Mechanisms of Uranyl–Peroxide Capsules from Monomers

Self-assembly of uranyl peroxide polyoxometalates (POMs) in alkaline peroxide solutions has been known for almost a decade, but in these dynamic solutions that contain high concentrations of base and peroxide the reaction pathway could never be discerned, mixed species are obtained, and reproducibility is sometimes a challenge. Here we elucidate the reaction mechanisms utilizing self-assembly of the U24 cluster, [UO2(O2)(OH)]24 24‑, from monomers as a model system. Using Raman as our main spectroscopic probe, we learned that the monomeric species is persistent in water at room temperature indefinitely. However, if a redox-active transition metal catalyst (copper (Cu2+) or cobalt (Co2+)) is added, self-assembly is accelerated in a significant manner, forming U24 peroxide clusters in several hours, which is a good time scale for studying reaction mechanisms. From semiquantitative treatment of the spectroscopic data, we elucidate reaction mechanisms that are consistent with prior structural and computational studies that suggest uranyl peroxide rings templated by alkalis are the building units of clusters. By understanding aqueous speciation and processes, we are moving toward assuming control over cluster self-assembly that has been mastered for decades now in the analogous transition-metal POM systems.