Sulfone‐functionalized stable molecular single crystals for photocatalytic hydrogen evolution

Highly crystalline organic semiconductors are ideal materials for photocatalytic hydrogen evolution in water splitting. However, the instability and complex synthesis processes of most reported organic molecule‐based photocatalysts restrict their applications. In this study, we introduce benzo [1,2‐b:4,5‐bʹ] bis [1] benzothiophene‐3,9‐dicarboxylic acid, 5,5,11,11‐tetraoxide (FSOCA), a highly crystalline, stable molecular crystal that is easy to synthesize and serves as an efficient photocatalyst for the hydrogen evolution reaction. FSOCA exhibits high efficiency in sacrificial hydrogen evolution reaction (760 µmol h−1, 76 mmol g−1 h−1 at 330 mW cm−2; 570 µmol h−1, 57 mmol g−1 h−1 at 250 mW cm−2), and FSOCA remains stable during photocatalysis for up to 400 h. Experiments and theoretical studies confirmed the presence of hydrogen bonds between the sulfone group and the sacrificial agent (ascorbic acid). This interaction significantly improved the oxidation reaction kinetics and boosted the photocatalytic performance. This study presents a scalable and convenient approach to synthesize highly crystalline, active, and stable organic photocatalysts with potential applications in large‐scale photocatalysis. Here, we report a sulfone‐functionalized molecular single crystal that integrates the necessary chemistry (high crystallinity, easy‐synthesized, and good stability) for efficient photocatalytic hydrogen evolution. The resulting materials show efficient hydrogen evolution at a rate of 76 mmol g−1 h−1 (λ > 320 nm), which can stably produce hydrogen for at least 400 h.