Bodipy-Containing Porous Microcapsules for Flow Heterogeneous Photocatalysis.

Abstract

Photocatalysis is a facile strategy for complex chemical transformations. Heterogeneous photocatalysis, especially in the flow system, has attracted much attention as it avoids the separation of catalysts. Herein, a kind of a Bodipy-containing porous microcapsule heterogeneous photocatalyst was rationally constructed with modulation on a multiscale. The diiodo-Bodipy with methacrylate (MA-2IBDP) was synthesized as a polymerizable photosensitizer. After immobilization in a polymer matrix, the intersystem crossing rate constant of MA-2IBDP increased to 2.7 × 1010 s-1 and its triplet excited-state lifetime prolonged to ∼1 ms. Porous structures in microcapsules were created to facilitate mass transfer. A flat plate flow reactor was constructed to fix the catalytic microcapsules and improve light utilization. With the combination of all the above benefits, the reaction rate constant (0.896 s-1) is 10 times faster than that of MA-2IBDP in a homogeneous system for juglone synthesis. The continuous production can last for 30 h without yield decrease. The photocatalyst can also be used in aza-Henry reaction, Alder-Ene reaction, and oxidation of thiols to disulfides with conversion rates above 95%. This study provides a means for the construction of heterogeneous catalysts and the flow reaction system.