Configurationally Confined Multilevel Supramolecular Assemblies for Modulating Multicolor Luminescence

Abstract Herein, multilevel supramolecular assemblies are reported based on sulfobutylether‐β‐cyclodextrin (SBE‐βCD) and cucurbit[8]uril (CB[8]), which can control the topological morphology from nanoparticles to nanosheets and modulate the multicolor luminescence. Benefiting from the large cavity of CB[8] and its strong binding affinity with positively charged tetraphenylethylene pyridinium (TPE‐Py), a 1:2 stoichiometric supramolecular assembly is formed through host–guest interactions with binding constants of 2.95 × 10¹¹ M⁻² and fluorescence bathochromic shift about 35 nm due to the macrocyclic confinement effect, thereby endowing the fluorescence enhancement about 20 times when further assembled with negatively charged SBE‐βCD to form nanosheets through electrostatic interactions. In contrast, the direct assembly of TPE‐Py and SBE‐βCD can form nanoparticles through electrostatic interactions, showing only tenfold enhancement and no bathochromic shift due to the lack of macrocyclic confinement effect. After doping the near‐infrared dye acceptor sulfonated aluminum phthalocyanine (AlPcS4), the nanosheets structure exhibits a higher energy transfer efficiency of about 75% and a larger antenna effect of 29.3 than that of nanoparticles. The multilevel supramolecular assemblies can be used in multicolor luminescence information storage and multiple logical gate systems, providing an efficient approach for configurationally confined topological morphology regulation and luminescent materials.