Biomimetic Hierarchical Construction of Anti‐Tumor Polyoxopalladates for Cancer Therapy

Abstract Inspired by the construction scheme of biomacromolecules, a hierarchical assembly based on the lacunary polyoxopalladate (POP) of [SrPd 12 O 6 (OH) 3 (PhAsO 3 ) 6 (OAc) 3 ] 4− (SrPd 12 ) has been achieved. As a structurally programmable molecular building block, SrPd 12 is used to evolve from monomer via dimer to supramolecular aggregates in a controlled manner. In such process, the open‐shell‐type monomers are covalently integrated into bowl‐ or cage‐like dimers via a direct or indirect splicing strategy. Upon that, hydrogen bond and hydrophobic effects are further hired to fabricate supramolecular aggregates of varied host–guest archetypes, thereby completing a hierarchical construction. In consideration of the combined advantages of noble metals and polyoxometalates in cancer treatment, both in vitro and in vivo anti‐tumor assays of these SrPd 12 ‐derived POPs were studied in detail. A structure‐dependent anti‐tumor activitywas observed, originating from an imbalance of damage and repair of DNA as anti‐tumor mechanism.