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A Hexadecacationic Metal–Organic Cage for Anchoring Sulfonates: High-Order Binding of Di- and Trisulfonates and High-Performance Removal of Perfluorosulfonates from Water

par Liu, Yawei;Li, Gen;Zhang, Xiang;Du, Zelin;Zhang, Tingting;Zhang, Yongya;Lavendomme, Roy ;Gao, En-Qing;Zhang, Dawei
Référence Advanced Science, 13, 1, e15258
Publication Publié, 2026-01-05

Article révisé par les pairs

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Résumé :

Developing synthetic hosts capable of binding sulfonate anions or sequestering perfluorosulfonates is highly important. In this work, the self-assembly of a tripyridinium-tricarboxylate ligand with Cp2ZrCl2 (Cp = η5-C5H5) is reported, yielding a highly cationic tetrahedral cage (1) engineered with acidic C−H protons. The hexadecacationic cage binds a variety of sulfonate anions with unprecedented charge-discriminative phenomena: the cage binds monosulfonates in fast exchange on the NMR timescale, while di- and multisulfonates exhibit slow-exchange binding. In particular, high-capacity complexation of di- and trisulfonates by 1 is achieved, with the pronounced case of 1 accommodating three dianions. Molecular modeling suggests the existence of a “Y”-shaped binding pocket on each edge of tetrahedron 1 (six in total), with each pocket capable of anchoring a guest bearing at least two sulfonate headgroups through electrostatic and hydrogen bonding interactions. Further investigations demonstrate that 1 in solid state is an exceptional adsorbent for perfluorooctane sulfonate (PFOS), with a maximum adsorption capacity of up to 1603 mg g−1 positioning it among the top PFOS adsorbents. Moreover, cage 1 exhibits rapid kinetics, high selectivity, and long-life cycles in PFOS removal, and also effectively adsorbs shorter perfluorosulfonates.