Dibenzothiophene‐S,S‐Dioxide‐Based Conjugated Polymers: Highly Efficient Photocatalyts for Hydrogen Production from Water under Visible Light

Three dibenzothiophene‐ S , S ‐dioxide‐based alternating copolymers were synthesized by facile Suzuki polymerization for visible light–responsive hydrogen production from water (> 420 nm). Without addition of any cocatalyst, FluPh2‐SO showed a photocatalytic efficiency of 3.48 mmol h −1 g− 1 , while a larger hydrogen evolution rate (HER) of 4.74 mmol h −1 g −1 was achieved for Py‐SO, which was ascribed to the improved coplanarity of the polymer that facilitated both intermolecular packing and charge transport. To minimize the possible steric hindrance of FluPh2‐SO by replacing 9,9′‐diphenylfluorene with fluorene, Flu‐SO exhibited a more red‐shifted absorption than FluPh2‐SO and yielded the highest HER of 5.04 mmol h −1 g −1 . This work highlights the potential of dibenzothiophene‐ S , S ‐dioxide as a versatile building block and the rational design strategy for achieving high photocatalytic efficiency.