The present study demonstrates the development of a supramolecular porous ensemble consisting of hetero‐oligophenylene derivative 6 and Au‐Fe3O4 nanodots. Supramolecular assemblies of AIE‐active hetero‐oligophenylene derivative 6 served as reactors for the generation of Au‐Fe3O4 nanodots. The as prepared supramolecular ensemble functioned as an efficient recyclable photocatalytic system for C(sp2)−H bond activation of anilines for the construction of quinoline carboxylates. Interestingly, the “dip catalyst” prepared by depositing PTh‐co‐PANI‐6: Au‐Fe3O4 nanodots on a filter paper served as a recyclable strip (up to 10 cycles) for C−C/C−N bond formation reaction.

The utilization of Pd nanoparticles stabilized by aggregates of hetero-oligophenylene derivative 3 as an excellent catalyst in a copper/amine free Sonogashira coupling reaction under aerial conditions at room temperature has been demonstrated.

The present study demonstrates the important role of alcohols themselves as electron donors for their oxidative transformations to the corresponding carbonyl compounds in the absence of any metal/oxidant and external photosensitizer.