Template-Directed Fabrication of Highly Efficient Metal-Organic Framework Photocatalysts.

Photocatalysis is a powerful and versatile tool widely applied in the areas of synthesis chemistry. However, most of the photocatalysts currently used are homogeneous catalysts, which inevitably face issues such as product-catalyst separation and recyclability. Addressing this challenge, we utilized a homogeneous Ru photocatalyst as a structure-directing template to fabricate a series of isostructural photocatalyst-encapsulating metal-organic frameworks (photocatalyst@MOFs) with high porosity, robustness, and photocatalyst loading. The regular channels of MOF can disperse the encapsulated photocatalysts, promote the mass transfer of substrates and products, and provide an outstanding substrate confinement effect, thereby dramatically improving the catalytic activity and excellent recyclability toward valuable organic reactions. For instance, the MOF photocatalysts can catalyze the asymmetric Mannich reaction with ketones with high yields and excellent enantioselectivities (up to 99% ee), better than the reported photocatalyst. Significantly, this was the first case that heterogeneous MOF-based photocatalyst can catalyze the asymmetric Mannich reaction without cocatalysts under room temperature and visible light. This work not only explores an avenue to prepare heterogeneous photocatalysts but also broadens the application scope of MOF-based photocatalysts.