Aqueous polycavity hosts composed of porous aromatic polymers within aromatic micelles

<h2>Summary</h2> Porous aromatic/polyaromatic polymers (PAPs) have been widely investigated as polycavity materials, featuring infinite grid frameworks with high stability. However, in contrast to host-guest functions in mono/oligocavities, the applications of these polycavities remained largely limited, owing to the complete insolubility, ill-defined structures, and inseparability. Here, we report a general strategy for the facile preparation of aqueous polycavity hosts through uptake of insoluble PAPs within aromatic micelles in water. The obtained aqueous host-guest composites, e.g., including a pyrene-benzene-based PAP, are analyzed via solution/solid-state techniques, revealing roughly spherical ∼100 nm-sized particles. The giant composites can be easily size fractionated in a highly monodisperse fashion using a centrifugation-filtration protocol. Importantly, the water-soluble polycavities of the PAPs within the micelle provide cavity-dependent incorporation abilities toward hydrocarbons, accompanying large emission enhancement (up to ∼9-fold) of the semi-rigid polycavities. Medium-sized dyes and hydrocarbons are furthermore co-incorporated into the polycavities, yielding unusual quaternary host-guest composites with enhanced dye-based emission.