Synergistic Effect over Sub-nm Pt Nanocluster@MOFs Significantly Boosts Photo-oxidation of N-alkyl(iso)quinolinium Salts.

Quinolones and isoquinolones are of interest to pharmaceutical industry owing to their potent biological activities. Herein, we first encapsulated sub-nm Pt nanoclusters into Zr-porphyrin frameworks to afford an efficient photocatalyst Pt0.9@PCN-221. This catalyst can dramatically promote electron-hole separation and 1O2 generation to achieve synergistic effect first in the metal-organic framework (MOF) system, leading to the highest activity in photosynthesis of (iso)quinolones in >90.0% yields without any electronic sacrificial agents. Impressively, Pt0.9@PCN-221 was reused 10 times without loss of activity and can catalyze gram-scale synthesis of 1-methyl-5-nitroisoquinolinone at an activity of 175.8 g·gcat−1, 22 times higher than that of PCN-221. Systematic investigations reveal the contribution of synergistic effect of photogenerated electron, photogenerated hole, and 1O2 generation for efficient photo-oxidation, thus highlighting a new strategy to integrate multiple functional components into MOFs to synergistically catalyze complex photoreactions for exploring biologically active heterocyclic molecules.