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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. A 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 ZrCl 4 , is reported herein to be efficient for the aerobic cross-dehydrogenative carbon-phosphorus coupling reaction, giving rise to a high turn-over number (TON) up to 17200 under visible light irradiation (longer than 420 nm). The electron paramagnetic resonance (EPR) experiments disclose that the active species might be the superoxide radical anion (O 2 ˙ - ). Additionally, the intermediate imine cation has been detected by the high resolution mass spectrum (HRMS).