Engineering porphyrinic MOFs via in-situ N–H chlorination for HOCl generation, detoxification, phototheranostics and antimicrobial activity

Integration of reactive chlorine chemistry into porous frameworks has been pursued by researchers in both materials science and biomedical fields, and has been realized in traditional catalyst systems. However, the in-situ controlled chlorination within metal-organic frameworks (MOFs) for multifunctional therapeutic platforms has not yet been explored.

Here, the authors report a porphyrin-based zirconium metal-organic framework, PCN-222-Cl, and we demonstrate the controlled N–H chlorination of porphyrin ligands using NaDCC. The formation of electron-withdrawing N–Cl bonds significantly increases the electron-deficient character of the porphyrin macrocycle, enabling efficient catalytic oxidation of chloride ions under mildly acidic to neutral conditions, accompanied by electronic reconfiguration synergistically coupled with Lewis-acidic Zr6O₄(OH)₄ nodes and an intrinsic photothermal response.

This work provides a generalizable strategy to engineer porphyrinic frameworks for multifunctional reactive chlorine chemistry and opens a way to integrate catalytic, photothermal, and oxidative properties for enhanced antibacterial, detoxifying, and antitumor applications. The work entitled “Engineering Porphyrinic MOFs via In-Situ N–H Chlorination for HOCl Generation, Detoxification, Phototheranostics and Antimicrobial Activity” was published in Advanced Powder Materials (available online on 2 July 2026).