Abstract: Cyanoarene photocatalysts such as 3DPAFIPN are widely employed in visible-light-driven transformations, yet their intrinsic structural dynamics under irradiation remain poorly understood. Here we reveal that 3DPAFIPN undergoes light-induced reconfiguration into distinct cyclized and radical substitution products, with the parent species ultimately decomposing under reaction conditions. Using a combination of Photo-Chem-ESI-MS and TLC-mapping, we directly monitored the evolution of catalytic forms and identified the cyclized derivatives as the true active species in thiol–yne–ene coupling. The major cyclized product was isolated and structurally confirmed by single-crystal X-ray diffraction, providing unambiguous experimental evidence for light-driven photocatalyst reconfiguration. Compared with the precursor, the cyclized catalysts display enhanced stability against cyanide substitution by radical intermediates and deliver higher efficiency and selectivity. This study establishes a generalizable workflow for dissecting dynamic photocatalyst behavior and extends the ReAct-Light concept, highlighting light-triggered structural evolution as a new design principle for adaptive and robust photocatalytic systems.

Cite: Burykina J.V. , Shlapakov N.S. , Kobelev A.D. , Chadin A.A. , Ananikov V.P.
Light‐Driven Preactivation of 3DPAFIPN into Highly Active Photocatalytic Species
Chemistry: A European Journal. 2025. e03363 . DOI: 10.1002/chem.202503363 WOS Scopus OpenAlex

Identifiers:

Web of science:	WOS:001651624500001
Scopus:	2-s2.0-105026398071
OpenAlex:	W7117763385

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