LAUSR

A global challenge faced by light harvesting photocatalyst is how to promote the selective organic transformation, such as C‐S bond formation via radical–radical coupling under solar light. Here, we report a two‐dimensional covalent organic frameworks (2D‐COFs), poly (perylene‐imide‐benzoquinone) nanorod through in situ condensation on flexible activated carbon cloth (PPIBNR‐FACC) to function as a light harvester material for highly selective radical–radical coupling to vinyl sulfides (i.e. C‐S bond activation). Such a structure supports charge transfer from PPIBNR to FACC, which is essential for the selective radical–radical coupling. Hence, organic transformation is attaining high yields and selectivity (˜99%) under solar light using in situ prepared PPIBNR‐FACC photocatalyst. The structural virtues of PPIBNR‐FACC will trigger the utmost investigations into designable and versatile 2D‐COFs for fine chemical synthesis.