Biomimetic Hierarchical Construction of Anti‐Tumor Polyoxopalladates for Cancer Therapy

In the light of the construction scheme of biomacromolecules, a hierarchical assembly based on lacunary polyoxopalladate (POP) of [SrPd12O6(OH)3(PhAsO3)6(OAc)3]4– (SrPd12) has been achieved. As a molecular building block that is structurally programmable, SrPd12 could evolve from monomer via dimer to supramolecular aggregate in a controlled manner. In such process, the open‐shell‐type monomers can be covalently integrated into bowl‐ or cage‐like dimers via a direct or indirect splicing strategy. Upon that, hydrogen bond and hydrophobic effect 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 metal and polyoxometalate in cancer treatment, both in vitro and in vivo anti‐tumor assays of these SrPd12‐derived POPs have been studied in detail. A structure‐dependent anti‐tumor activity has been observed, along with the disclosure of the imbalance of damage and repair of DNA as anti‐tumor mechanism.