A Porphyrin‐Based 3D Metal‐Organic Framework Featuring [Cu₈Cl₆]¹⁰⁺ Cluster Secondary Building Units: Synthesis, Structure Elucidation, Anion Exchange, and Peroxidase‐Like Activity

Herein, we report a rare example of cationic three‐dimensional (3D) metal‐organic framework (MOF) of [Cu 5 Cl 3 (TMPP)]Cl 5 ⋅ x Sol (denoted as Cu−TMPP ; H 2 TMPP= meso ‐tetrakis (6‐methylpyridin‐3‐yl) porphyrin; x Sol=encapsulated solvates) supported by [Cu 8 Cl 6 ] 10+ cluster secondary building units (SBUs) wherein the eight faces of the Cl − ‐based octahedron are capped by eight Cu 2+ . Surface‐area analysis indicated that Cu−TMPP features a mesoporous structure and its solvate‐like Cl − counterions can be exchanged by BF 4 − , PF 6 − , and NO 3 − . The polyvinylpyrrolidone (PVP) coated Cu−TMPP (denoted as Cu−TMPP−PVP ) demonstrated good ROS generating ability, producing ⋅OH in the absence of light (peroxidase‐like activity) and 1 O 2 on light irradiation (650 nm; 25 mW cm −2 ). This work highlights the potential of Cu−TMPP as a functional carrier of anionic guests such as drugs, for the combination therapy of cancer and other diseases.