Abstract
<jats:p> Photoredox catalysis is commonly described through the behavior of a formally defined catalyst that is assumed to retain its molecular identity throughout turnover. The present study shows that this picture is incomplete for the widely used cyanoarene photocatalyst 3DPA2FBN. Under visible-light irradiation, 3DPA2FBN is consumed rapidly and evolves into a limited yet functionally differentiated ensemble of photoderivatives. The <jats:italic toggle="yes">operando</jats:italic> transformation pattern is strikingly similar across distinct reaction classes, indicating that the earliest stages of catalyst evolution are governed mainly by intrinsic, substrate-independent processes encoded in the photocatalyst itself. This behavior is captured here by the concept of photocatalyst orthogonality. Isolation, spectroscopic characterization, X-ray analysis, photocatalytic benchmarking, and DFT calculations identify three major states generated from the 3DPA2FBN prototype: the ortho-cyclized photocatalyst <jats:sup>o-Ind</jats:sup> 2DPAFBN ( <jats:bold>PC-2.0</jats:bold> ), the para-cyclized photocatalyst <jats:sup>p-Ind</jats:sup> 2DPAFBN ( <jats:bold>PC-2.1</jats:bold> ), and the bicyclized product <jats:sup>o,p-Ind</jats:sup> DPABN ( <jats:bold>post-PC</jats:bold> ). These species are not functionally equivalent. <jats:bold>PC-2.0</jats:bold> emerges as the dominant stable productive state, combining high activity with exceptional resistance to further degradation and sustained performance at ultralow catalyst loading. <jats:bold>PC-2.1</jats:bold> is a transient high-reactivity state that is gradually converted into <jats:bold>post-PC</jats:bold> , whereas <jats:bold>post-PC</jats:bold> behaves as a catalytically incompetent terminal form in the benchmark systems examined here. Computations support triplet-state anti-cyclization as the principal activation pathway and explain both the competition between the ortho- and para-cyclization routes and the kinetic trapping of <jats:bold>PC-2.0</jats:bold> . Taken together, the results redefine 3DPA2FBN from a static photocatalyst into a photocatalyst prototype that self-edits under operational conditions into second-generation catalysts with exceptional efficiency characteristics. This mechanistic picture provides a practical framework for designing more robust cyanoarene photocatalysts by targeting operationally selected catalyst states rather than only the initial precatalyst structure. </jats:p>