Though Olefin-linked covalent organic frameworks (oCOFs) possess excellent π-electron delocalization, the barely reversible olefin linkage brings challenges for oCOFs’ synthesis and functionalization. Here, we synthesize new oCOFs with tertiary amine knots which have twisted configuration and electron-donating nature. Investigation into the structural variation and photoelectric performance shows that the twisted configuration of oCOF-TFPA could favor to the intramolecular charge transfer process and reduce the possibility of aggregation-caused quenching. Photoelectrical measurements and electric band structure calculation both verify the superiority of this oCOFs’ structure in photoelectric sensing.

尽管烯烃连接的共价有机框架（oCOFs）具有优异的π电子离域性，但几乎不可逆的烯烃连接给oCOFs的合成和功能化带来了挑战。在这里，我们合成了具有扭曲构型和供电子性质的叔胺结的新型 oCOF。对结构变化和光电性能的研究表明，oCOF-TFPA的扭曲构型有利于分子内电荷转移过程，降低聚集引起猝灭的可能性。光电测量和电带结构计算均验证了该oCOFs结构在光电传感方面的优越性。