Vinylene‐Linked Covalent Organic Frameworks for Visible‐Light‐Promoted Selective Oxidation of Styrene in Water

Abstract Vinylene‐linked COFs, as an emerging class of crystalline porous polymers, have been regarded as ideal heterogenous photocatalysts due to their ordered structure, tailored pore size, outstanding stability and fully π ‐conjugated structure. Unfortunately, their photocatalytic performances are usually impeded by high exciton binding energy and unsatisfactory exciton dissociation efficiency. Herein, the authors broke through this dilemma by arrangement of complementary donor–acceptor (D–A) pairs within the COF skeleton to improve charge transfer/separation. Two vinylene‐linked COFs (TMT‐BT‐COF and TMT‐TT‐COF) are synthesized by Aldol condensation using highly photoactive thienothiophene and benzothiazole groups as donor and electron‐deficient triazine units as acceptor. Photochemical/electrochemical studies as well as DFT calculation suggest that these D–A type vinylene‐linked COFs endow high charge transfer efficiency and low charge recombination. As a result, both of them demonstrate remarkably catalytic activity in the oxidation of styrene to benzaldehyde with molecular oxygen, with an exceptionally high conversion rate (≥92%) and selectivity (≥90%). Intriguingly, in the presence of NaHCO 3 , the above COFs could photocatalyze epoxidation styrene in water, and the styrene oxide selectivity reached 53%. This work elucidates the prominent capability of vinylene‐linked COFs in the photocatalytic transformation of organic compounds in aqueous media, which may pave a new avenue for their future development.