A Porous and Stable Porphyrin Metal‐Organic Framework as an Efficient Catalyst towards Visible‐Light‐Mediated Aerobic Cross‐Dehydrogenative‐Coupling Reactions

Porphyrin metal‐organic frameworks (PMOFs) are emerging as heterogeneous photocatalysts owing to the well‐designed frameworks incorporated with powerful light‐harvesting porphyrin chromophores. The porous and stable framework Ir?PCN‐224 (which is also denoted as Ir?PMOF‐1), which has been prepared by the self‐assembly of Ir(TCPP)Cl (TCPP=tetrakis(4‐carboxyphenyl)porphyrin) and ZrCl₄, is reported herein to be efficient for the aerobic cross‐dehydrogenative carbon?phosphorus coupling reaction, giving rise to a high turn‐over number (TON) of up to 17200 under visible light irradiation (λ≥420 nm). Electron paramagnetic resonance (EPR) experiments disclose that the active species might be the superoxide radical anion (O₂^.?). Additionally, the intermediate imine cation has been detected by high‐resolution mass spectrometry (HRMS).