Molecular Engineering of Fully Conjugated sp2 Carbon‐Linked Polymers for High‐Efficiency Photocatalytic Hydrogen Evolution

The diverse nature of organic precursors offers a versatile platform for precisely tailoring the electronic properties of semiconducting polymers. In this study, three fully conjugated sp² carbon-linked polymers have been designed and synthesized for photocatalytic hydrogen evolution under visible-light illumination, by copolymerizing different C₃ -symmetric aromatic aldehydes as knots with the 1,4-phenylene diacetonitrile (PDAN) linker through a C=C condensation reaction. The hydrogen evolution (HER) is achieved at a maximum rate of 30.2 mmol g^-1 h^-1 over a polymer based on 2,4,6-triphenyl-1,3,5-triazine units linked by cyano-substituted phenylene, with an apparent quantum yield (AQY) of 7.20 % at 420 nm. Increasing the degree of conjugation and planarity not only extends visible-light absorption, but also stabilizes the fully conjugated sp² -carbon-linked donor-acceptor (D-A) polymer. Incorporating additional electron-withdrawing triazine units into the D-A polymer to form multiple electron donors and acceptors can greatly promote exciton separation and charge transfer, thus significantly enhancing the photocatalytic activity.