There is growing interest in developing triplet photosensitizers in terms of implementing photochemical strategies in synthetic chemistry. However, synthesis of stable triplet organic photosensitizers is nontrivial and often requires the use of heavy atoms. Herein, an alternative strategy is demonstrated to enhance the triplet generation efficiency by implanting lone-pair donor-acceptor bonds in the conjugated covalent organic frameworks (COFs). This powerful method is validated using COFs that host triazine, a moiety that has been extensively investigated in photocatalysis. Spectroscopic analysis and theoretical calculations reveal substantial improvements in the photoabsorptivity and triple-state photogeneration efficiency, consistent with catalytic tests concerning industrially relevant sulfide oxidation. These systems represent a promising addition to the rapidly increasing arsenal of synthetic photocatalytic systems.

Aryl-ketone derivatives have been acknowledged as promising organic photocatalysts for photosynthesis. However, they are limited by their photostability and have been less explored for photoinduced electron transfer (PET) applications. Herein we demonstrate a novel strategy to cover the shortage of aryl-ketone photocatalysts and control the photoreactivity by implanting symmetric aryl ketones into the conjugated covalent organic frameworks (COFs). To prove the concept, three comparative materials with the same topology and varied electronic structures were built, adopting truxenone knot and functionalized terephthalaldehyde linkers. Spectroscopic investigation and excited carrier dynamics analysis disclosed improvements in the photostability and electronic transfer efficiency as well as the structure−performance relationships toward N-aryl tetrahydroisoquinoline oxidation. This system provides a robust rule of thumb for designing new-generation aryl-ketone photocatalysts.