The novel phenothiazine-linked covalent triazine framework (CTF, named as TPDH-PTBA), as well as the benzene- or triazine-linked counterparts (named as TPDH-TFPB and TPDH-TAPT, respectively), have been synthesized via direct polycondensation of terephthalimidamide and trisformyl precursors in DMF. Characterization of these three CTFs indicated the formation of macrocycle rings that were formed via covalently linked phenothiazine (or benzene) and triazine units. Among the CTFs, TPDH-PTBA with phenothiazine units exhibited a relatively broad band gap of ∼2.08 eV and excellent photocatalytic activity towards aerobic oxidation reactions. Specifically, the conversion rates of photocatalytic benzylamine coupling and anisothioether oxidation reactions by TPDH-PTBA were almost 100%, significantly higher than those of TPDH-TFPB and TPDH-TAPT. We proposed a photocatalytic pathway of these CTFs based on the experimental and theoretical evidences. Our findings highlight the potential of structural design at the molecular level to improve the intrinsic properties and photocatalytic performance of CTFs. These resulting porous organic polymers offer promise for green and sustainable application in organic synthesis and pollutant degradation.

新型吩噻嗪连接的共价三嗪框架（CTF，命名为 TPDH-PTBA）以及苯或三嗪连接的对应物（分别命名为 TPDH-TFPB 和 TPDH-TAPT）是通过直接缩聚合成的DMF 中的对苯二甲酰亚胺和三甲酰基前体。这三个 CTF 的表征表明，通过共价连接的吩噻嗪（或苯）和三嗪单元形成了大环环。在CTF中，具有吩噻嗪单元的TPDH-PTBA表现出相对较宽的带隙（约2.08 eV）和对有氧氧化反应优异的光催化活性。具体而言，TPDH-PTBA的光催化苯甲胺偶联和异硫醚氧化反应的转化率几乎为100%，显着高于TPDH-TFPB和TPDH-TAPT。我们根据实验和理论证据提出了这些 CTF 的光催化途径。我们的研究结果强调了分子水平结构设计在改善 CTF 的固有特性和光催化性能方面的潜力。这些所得的多孔有机聚合物为有机合成和污染物降解领域的绿色和可持续应用提供了前景。