Self‐Assembly and Aggregation‐Induced Emission in Aqueous Media of Responsive Luminescent Copper(I) Coordination Polymer Nanoparticles

Luminescent copper(I)‐based compounds have recently attracted much attention since they can reach very high emission quantum yields. Interestingly, Cu(I) clusters can also be emissive, and the extension from small molecules to larger architecture could represent the first step towards novel materials that could be obtained by programming the units to undergo self‐assembly. However, for Cu(I) compounds the formation of supramolecular systems is challenging due to the coordinative diversity of copper centers. This works shows that this diversity can be exploited in the construction of responsive systems. In detail, the changes in the emissive profile of different aggregates formed in water by phosphine‐thioether copper(I) derivatives were followed. Our results demonstrate that the self‐assembly and disassembly of Cu(I)‐based coordination polymeric nanoparticles (CPNs) is sensitive to solvent composition. The solvent‐induced changes are related to modifications in the coordination sphere of copper at the molecular level, which alters not only the emission profile but also the morphology of the aggregates. Our findings are expected to inspire the construction of smart supramolecular systems based on dynamic coordinative metal centers. Stable copper(I) coordination polymer nanoparticles (CPNs) are self‐assembled in water and they display solvent composition‐responsive behavior that can be followed by emission of the aggregates. The dramatic differences in the emission energy and the morphology of the aggregates have been attributed to changes in the coordination sphere around the copper centers.