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

• Published in: Chemistry, an Asian journal Vol. 15; no. 7; pp. 1118 - 1124
• Main Authors: Liu, Jiewei, Zhang, Kun, Chen, Zhiyao, Wei, Zhang‐Wen, Zhang, Li
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.04.2020
• Subjects: aerobic cross dehydrogenative coupling; carbon−phosphorus coupling; Chemical reactions; Chemistry; Chromophores; Coupling; Dehydrogenation; Electron paramagnetic resonance; heterogeneous catalysis; Light irradiation; Mass spectrometry; porphyrin metal-organic frameworks; superoxide radical anion; carbon−phosphorus coupling; superoxide radical anion; porphyrin metal-organic frameworks; heterogeneous catalysis; aerobic cross dehydrogenative coupling
• ISSN: 1861-4728; 1861-471X; 1861-471X
• DOI: 10.1002/asia.201901697

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). An iridium(III) porphyrin‐based metal‐organic framework acts as an efficient photocatalyst for the aerobic cross‐dehydrogenative carbon−phosphorus coupling reaction.