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Strong excitonic effects, induced by the Coulombic interactions between photogenerated electrons and holes, seriously hinder the generation of free charge carriers in organic semiconductors for conducting photocatalysis. Herein, we report a built-in control of the donor–acceptor (D–A) interaction strategy to regulate excitonic effects within benzobisthiazole-bridged covalent organic frameworks (Tz-COFs). Theoretical calculation and ultrafast spectroscopy reveal that strengthening D–A interactions by this built-in control strategy in Tz-COFs can accelerate exciton dissociation, thus generating more long-lived photogenerated charge carriers for photoredox reactions. As a result, the optimized Tz-COF-3 exhibits high photocatalytic H2 evolution activity as high as 43.2 mmol g–1 h–1, with an apparent quantum yield of 6.9% at 420 nm. This work guides the development of COFs from excitonic aspects for photocatalysis.
Liu et al. (Wed,) studied this question.