Enhanced C(sp3)–H Selective Oxidation Using Efficient Polyoxometalate-Based Metal–Organic Framework Photocatalysts Synergized with Ir Metalloligands and Polyoxometalates

Achieving efficient selective visible light-induced oxidation of benzyl C(sp³)–H to more valuable double-bonded compounds holds significant promise for organic synthesis. In this work, we fabricated an example of Ir metalloligand-modified POMOF crystalline material, CI-SiW, which is noteworthy as the first example of POM immobilized in a metalloligand-modified MOF via coordination bonding. Under the excitation of visible light (10 W, λ = 410 nm), CI-SiW can catalyze the efficient oxidation of benzyl C(sp³)–H of isochromane with a turnover number and turnover frequency of 954 and 1740 h^–1, respectively. Excitingly, CI-SiW displays the best TOF compared with previous photocatalysts under the same conditions, realizing the maximum yield with the minimum amount of photocatalyst. Furthermore, CI-SiW had good cyclic and structural stability, and a 90.4% yield was still obtained after three reaction cycles.