In this study, we discovered the photoredox autocatalytic pathway towards BASNthis further supported the use of BASN as a photocatalyst together with the abovementioned blueprint (Figure ). In other words, as BASN can act as a photocatalyst for its own formation, logic follows that it could be employed as a photocatalyst for other reactions. Exploiting the ease of synthesis of BASN, a rapid combinatorial design allowed one-pot, in situ generation of diverse BASN photocatalysts from inexpensive, easily accessible building blocks. This photocatalyst library was then directly screened in photo-reductive transformations and as such this design enabled rapid identification of the optimal photocatalyst structure. Through high-throughput reaction screening, we tested BASN's applicability to catalyze diverse transition metal-free radical transformations (Figure ) such as: i) intramolecular (spiro)-cyclizations, ii) defunctionalizations, and iii) C-C / C-heteroatom couplings.