Precise Post-Synthetic Modification of Heterometal-Organic Capsules for Selectively Encapsulating Tetrahedral Anions

Post-synthetic modification plays a crucial role in precisely adjusting the structure and functions of advanced materials. Herein, we report the self-assembly of a tubular heterometallic Pd₃Cu₆L1₆ capsule that incorporates Pd(II) and CuL1 metalloligands. This capsule undergoes further modification with two tridentate anionic ligands (L2) to afford a bicapped Pd₃Cu₆L1₆L2₂ capsule with an Edshammer polyhedral structure. By employing transition metal ions, acid, and oxidation agents, the bicapped capsule can be converted into an uncapped one. This uncapped form can then revert back to the bicapped structure on the addition of Br^- ions and a base. Interestingly, introducing Ag⁺ ions leads to the removal of one L2 ligand from the bicapped capsule, yielding a mono-capped Pd₃Cu₆L1₆L2 structure. Furthermore, the size of the anions critically influences the precise control over the post-synthetic modifications of the capsules. It was demonstrated that these capsules selectively encapsulate tetrahedral anions, offering a novel approach for the design of intelligent molecular delivery systems.