A Porphyrin-Based 3D Metal-Organic Framework Featuring [Cu 8 Cl 6 ] 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  ⋅ xSol (denoted as Cu-TMPP; H 2 TMPP=meso-tetrakis (6-methylpyridin-3-yl) porphyrin; xSol=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.