The study of nanocrystal self‐assembly into superlattices or superstructures is of great significance in nanoscience. Carbon nitride quantum dots (CNQDs), being a promising new group of nanomaterials, however, have hardly been explored in their self‐organizing behavior. Here we report of a unique irradiation‐triggered self‐assembly and recrystallization phenomenon of crystalline CNQDs (c‐CNQDs) terminated by abundant oxygen‐containing groups. Unlike the conventional self‐assembly of nanocrystals into ordered superstructures, the photoinduced self‐assembly of c‐CNQDs resembles a “click reaction” process of macromolecules, in which the activated ‐OH and ‐NH2 functional groups along the perimeters initiate cross‐linking of adjacent QDs through a photocatalytic effect. Our findings unveil fundamental physiochemical features of CNQDs and open up new possibilities of manipulating carbon nitride nanomaterials via controlled assembly. Prospects for potential applications are discussed as well.

The study of nanocrystal self‐assembly into superlattices or superstructures is of great significance in nanoscience. Carbon nitride quantum dots (CNQDs), being a promising new group of nanomaterials, however, have hardly been explored in their self‐organizing behavior. Here we report of a unique irradiation‐triggered self‐assembly and recrystallization phenomenon of crystalline CNQDs (c‐CNQDs) terminated by abundant oxygen‐containing groups. Unlike the conventional self‐assembly of nanocrystals into ordered superstructures, the photoinduced self‐assembly of c‐CNQDs resembles a “click reaction” process of macromolecules, in which the activated ‐OH and ‐NH2 functional groups along the perimeters initiate cross‐linking of adjacent QDs through a photocatalytic effect. Our findings unveil fundamental physiochemical features of CNQDs and open up new possibilities of manipulating carbon nitride nanomaterials via controlled assembly. Prospects for potential applications are discussed as well.