Cavity‐Partitioned Self‐Assembled Cage for Sequential Separation in Aqueous Solutions

The concept of pore space partition has emerged as an effective strategy for developing improved coordination‐based supramolecular porous materials with exceptional performance. Herein, we report that a water‐soluble self‐assembled tetrahedral cage 1 with a partitioned cavity shown excellent performance as a multifunctional extractant. The results show that this unique partitioned cavity can efficiently separate halogenated adamantanes, adamantane isomers, and polycyclic aromatic hydrocarbons. Furthermore, the influence of cavity‐partitioned cage 1 on the electrochemical properties of redox‐active molecules and electrochemically driven reversible host–guest process has also been demonstrated. The findings offer valuable insights into the design and development of new type of materials with controlled phase separation and tailored electrochemical properties. The partitioned cavity of cage 1 demonstrates a high degree of molecular‐specific recognition, enabling its application not only in the separation of adamantane derivatives but also in the progressive separation of multi‐component polycyclic aromatic hydrocarbons. Moreover, the reversible binding between the redox‐active guest and 1 is achieved through precise regulation of the reduction/oxidation state of the guest via electrochemical stimulation.