Structural Engineering of Donor−π–Acceptor Conjugated Polymers for Facilitating Charge Separation: A Dual-Functional Photocatalysis

Conjugated polymers have emerged in recent years as prospective organic semiconductors in solar energy conversion. However, developing highly efficient conjugated polymers is still a grand challenge. Herein, we first demonstrate the fabrication of two donor−π–acceptor (D−π–A) conjugated polymers (N-DEA-TBP and L-DEA-DBP) by incorporating redox-active anthraquinone into pyrene units through acetenyl linkages. Comprehensive experiments and density functional theory calculations reveal that the network-conjugated chain and acetenyl-bridged conjugated structure facilitate charge utilization and separation/transfer in the skeleton. Such advantages of N-DEA-TBP endow it with outstanding activity for the photoreduction of CO2 in H2O without a sacrificial agent and photosensitizer, affording CO as the sole carbonaceous product with a generation rate of 70.25 μmol·g–1·h–1 and nearly 100% selectivity, which is almost 2.6-fold as high as that of L-DEA-DBP. Furthermore, N-DEA-TBP also exhibits an attractive photocatalytic performance for selective aerobic oxidation of sulfides under visible light irradiation. This study contributes new insights into their underlying structure and morphology for enhancing charge separation and transfer.