Upgraded decatungstate: the visible-light-responsive, recyclable, and efficient photocatalyst achieved via self-assembly

Abstract

The rational design of high-performance, visible-light-responsive and recyclable C–H bond activation photocatalysts represents one of the critical challenges in advancing sustainable photocatalytic chemistry. Here, we successfully obtained a novel crystalline material (CdRu-DT or CR-DT) through the self-assembly of decatungstate (DT) with Ru metalloligands, which represents the first example of crystalline polyoxometalate@metal–organic frameworks incorporating DT with photosensitive metalloligands. CR-DT not only retains the hydrogen atom transfer (HAT) function of DT but also overcomes its limitations of being effective only in the ultraviolet light region and inefficient reusability, further enhancing its photocatalytic performance. When CR-DT was employed as a photocatalyst for the Baeyer–Villiger oxidation reaction, the catalytic generation of ε-caprolactone was achieved in yields up to 99.5%, with TON and TOF values of 995 and 678 h⁻¹, respectively. This TON represents the highest value among the photocatalysts currently used for the Baeyer–Villiger oxidation reaction. Remarkably, CR-DT exhibited excellent recyclability and maintained a high yield even after 10 cycles, thus proving to be a viable candidate for industrial applications.