Exciton tuning and charge steering in donor-acceptor covalent triazine frameworks toward boosted photocatalytic oxidation

Conventional heterogeneous photocatalysts often suffer from insufficient light absorption, rapid charge recombination, and a lack of specific reactive sites for efficient photocatalytic oxidation. To overcome these limitations, we propose a molecular polarization engineering approach utilizing structurally well-defined donor (D)-acceptor (A) covalent triazine frameworks (CTFs). The construction of dipole-induced built-in electric fields within the D-A-structured CTFs enables enhanced exciton dissociation and facilitates directional charge transfer. Specifically, the asymmetric A1-D-A2 moiety enhances molecular polarization in the dual-acceptor system CTF-TBT (A1-D-A2), enabling efficient charge separation through multiple electron-withdrawing units. This structural design promotes directional electron transfer toward the secondary acceptor (benzothiazole, A2), while simultaneously concentrating holes on the donor unit. Consequently, the A2 moiety acts as a site for efficient O2 activation via electron accumulation, whereas the highly oxidized donor unit provides strongly positive holes (h+) that facilitate substrate oxidation. Experimental and DFT calculation results confirm that CTF-TBT demonstrates highly enhanced photocatalytic oxidation performance, which can be attributed to its multi-channel charge separation mechanism and spatially separated redox-active sites. This study highlights the effectiveness of molecular dipole engineering in designing heterogeneous photocatalysts with controlled charge transfer pathways and improved redox capabilities. The proposed design principles provide a universal approach for promoting solar-driven chemical synthesis applications.