Tailoring the Degradation of Cyanoarene‐Based Photocatalysts for Enhanced Visible‐Light‐Driven Halogen Atom Transfer

We present the strategic design of donor-acceptor cyanoarene-based photocatalysts (PCs) aiming to augment beneficial PC degradation for halogen atom transfer (XAT)-induced dehalogenation reactions. Our investigation reveals a competitive nature between the catalytic cycle and the degradation pathway, with the degradation becoming dominant, particularly for less activated alkyl halides. The degradation behavior of PCs significantly impacts the efficiency of the XAT process, leading to exploration into manipulating the degradation behavior in a desirable direction. Recognizing the variation in the nature and rate of PC degradation, as well as its influence on the reaction across the range of PC structures, we carefully engineered the PCs to develop a pre-catalyst, named 3DP-DCDP-IPN. This pre-catalyst undergoes rapid degradation into an active form, 3DP-DCDP-Me-BN, exhibited an enhanced reducing ability in its radical anion form to induce better PC regeneration and consequently effectively catalyzes the XAT reaction, even with a challenging substrate.