Multicharged Cyclodextrin‐Based Supramolecular Assemblies for Efficient Light‐Harvesting Energy Transfer

Multicharged macrocyclic supramolecular assemblies have been widely used in luminescent materials. Herein, we constructed multicharged assemblies based on tetraphenylethylene pyridinium derivatives (TPE‐4Py, TPE‐4Bz) and sulfobutylether‐β‐cyclodextrin (SBE‐βCD) through multivalent interactions. TPE‐4Py can be assembled with SBE‐βCD to form nanoparticles with 5.9‐fold fluorescence enhancement by electrostatic interactions and π‐π interactions, displaying an energy transfer efficiency of 7% to Nile Red and an antenna effect value of 0.8. In contrast, TPE‐4Bz with four more benzyl groups exhibited superior assembly capacity with SBE‐βCD to form twisted nanosheets through additional hydrophobic interactions, resulting in enhancement of fluorescence intensity by 121 times. The TPE‐4Bz@SBE‐βCD can be served as a good light‐harvesting energy transfer platform to Nile Red with 87% energy transfer efficiency and an antenna effect value of 17.2. This multicharged supramolecular assembly strategy provides an effective method for the construction of assembling‐confined luminescent materials with different topological morphology.