Cucurbit[7]uril-Mediated 2D Single-Layer Hybrid Frameworks Assembled by Tetraphenylethene and Polyoxometalate toward...

Construction of large-scale single-layer two-dimensional (2D) frameworks in water is significant due to their utilities in various fields. Utilizing macrocycle-mediated supramolecular self-assembly represents a promising approach; however, challenges still remain in their practical preparation. Here, we exploited a two-step supramolecular strategy to build 2D organic-inorganic hybrid frameworks at a micrometer scale in water. Taking advantage of the high binding affinity to cucurbit[7]uril (CB[7]), mono-quaternary ammonium tetraphenylethene (MQATPE) derivatives were first included with CB[7] to form a 1:1 complex (MQATPE@CB[7]). Then, just mixing the complex with anionic polyoxometalate Na₉[EuW₁₀O₃₆]·32H₂O (denoted as Eu-POM) in a 3:1 molar ratio leads to the formation of single-layer 2D films with tens of micrometers via electrostatic and π-π stacking interactions. The most unique feature of this strategy is that the steric effect imposed by CB[7] would not only lead the modules to adopt a periodic hexagonal assembly but also forbid stacking between layers through comparison with the merely multilayered 2D nanosheets self-assembled by MQATPE/Eu-POM. Interestingly, the charge interactions between MQATPE and Eu-POM would lead to the aggregation-induced emission (AIE) fluorescence of MQATPE, and white light emission could be obtained through the simple regulation of the contents of Eu-POM and MQATPE. Furthermore, due to the high surface areas and more accessible active sites, the single-layer films can act as an effective enzyme inhibitor to modulate the activity of α-chymotrypsin (ChT). These findings suggest a simple but universal approach for single-layer hybrid materials, which may hold promise for practical applications in photophysical and biomedical fields.