Enhanced Carrier Separation in Visible-Light-Responsive Polyoxometalate-Based Metal-Organic Frameworks for Highly Efficient Oxidative Coupling of Amines.

Photocatalytic technology is widely studied, while it comes with drawbacks such as low sunlight utilization efficiency and high carrier recombination rates. Herein, for the first time, we present two crystalline polyoxometalate (POM)-based metal-organic frameworks (POMOFs), {[Cd(DMF) 2 Ru(bpy) 2 (dcbpy)] 2 (POMs)(DMF) 2 } x DMF ( PMo-1 , POMs = [PMo VI 11 Mo V O 40 ] 4- , x = 5; SiW-2 , POMs = [SiW 12 O 40 ] 4- , x = 4) through assembling the photosensitizer [Ru(bpy) 2 (H 2 dcbpy)]Cl 2 and POMs into a single framework. The assembly not only enhances light absorption in the visible light regime but also improves carrier separation efficiency; atop of that, both POMOFs demonstrate activities in the photocatalytic oxidative coupling of amines. Particularly, PMo-1 enables the quantitative completion of oxidative coupling of benzylamine reaction within 30 min (yield = 99.6%) with a high turnover frequency (TOF = 6631.6 h -1 ). To our knowledge, the PMo-1 catalyst outperforms any other photocatalysts previously reported in similar use cases where TOF values were usually obtained <2000 h -1 .