image: Engineering metal-organic cages (MOCs) with metal acyl nodes utilizes the axial oxygen atoms of these nodes as complementary internal binding sites for the supramolecular recognition of metal ions. The resultant uranyl-based MOC (UOC) efficiently encapsulates Sr2+ within its cryptand-like cavity through metal-ligand coordination, thereby facilitating the selective removal of trace-level Sr2+. Furthermore, the hydrophobic cavities at both ends of the coordination cage in the UOC enable the recognition of organic guests and support the co-recognition of two types of guests within the same UOC.
Credit: ©Science China Press
Recently, Science Bulletin published the research findings of Professors Shi Weiqun and Mei Lei from the Institute of High Energy Physics, Chinese Academy of Sciences. The study presents a viable approach for engineering acyl-type metal nodes to create oxygen-rich interior sites within MOCs, enabling the specific recognition of metal ions, including radioactive contaminants, while preserving the structural integrity of the MOCs. A novel MOC, referred to as UOC, featuring a uranyl-sealed calix[4]resorcinarene (C[4]R)-based multisite cavity, was synthesized as a prototype. In UOC, peroxide-bridged dimeric uranyl units at both ends of the coordination cage provide abundant oxygen sites for coordination, forming a cryptand-like cavity that facilitates the efficient recognition and encapsulation of Sr2+ through a size-matching effect. Additionally, hydrophobic binding cavities at both ends of UOC facilitate the co-encapsulation of two distinct guest species. Inspired by the strong binding affinity of UOC for Sr2+, it was employed as a solid adsorbent to capture low concentrations of Sr2+ from strontium-contaminated simulated groundwater. A removal efficiency of 99.7% for Sr2+ at an initial concentration as low as 0.013 mmol L-1 was achieved, demonstrating its significant potential for the selective removal of trace amounts of radioactive 90Sr2+. In summary, this work demonstrates the feasibility of incorporating acyl-type metal nodes into MOCs for the recognition and encapsulation of metal ions, provides new insights into the design of precise recognition sites within MOC cavities, and proposes a novel strategy for developing materials to purify radioactive metals.
Journal
Science Bulletin