“One‐Pot” Synthesized Phosphorus Corrole‐Based Metal–Organic Frameworks for Synergistic Phototherapy and Chemodynamic Therapy

Abstract As a distinctive class of porphyrin derivatives, corroles offer exceptional potential in phototherapy applications owing to their unique electronic structures. However, developing metal–organic frameworks (MOFs) that incorporate photosensitive corroles as functional ligands for synergistic phototherapy remains a formidable challenge. Herein, for the first time, the unique phosphorus corrole‐based MOFs Cor(P)‐Hf with (3,18)‐connected gea topology are reported, which are constructed by Cs‐symmetric dicarboxylate 3‐connected linkers, 10‐pentafluorophenyl‐5,15‐di(p‐benzoate)phosphorus corrole (Cor(P)), and the peculiar D_3h‐symmetric 18‐connected Hf₁₂‐oxo clusters. Interestingly, six para‐position F substituents of six Cor(P) linkers are found to be coordinated with the apex of the Hf₁₂‐oxo cluster through Hf‐F bonds along the c‐axis direction, which is believed to help stabilize the framework. Furthermore, the mixed corrolic ligand‐based MOFs Cor(P)/Cor(Cu)‐Hf and Cor(P)/Cor(Fe)‐Hf involving Cor(Fe) or Cor(Cu) as the secondary functional linkers are constructed by a simple “one‐pot” solvent‐thermal method, respectively. Remarkably, Cor(P)/Cor(Fe)‐Hf facilitates synergistic phototherapy combining photodynamic therapy (PDT), photothermal therapy (PTT), and chemodynamic therapy (CDT) when activated by an 808 nm laser, as evidenced by in vivo and in vitro experiments. This study demonstrates corrole‐based MOFs Cor(P)‐Hf as a powerful multifunctional nanoplatform for anti‐cancer phototherapy.