Supramolecular Allostery Achieves Tunable Luminescence Aromatic Bridged Phenothiazine Noncovalent Frameworks.

Here, we report an engineering tunable luminescent supramolecular organic framework (SOF) enabled by multiple allosteric effects, composed of a tetracationic vinylphenylpyridinium-modified aromatic-bridged phenothiazine guest and cucurbit[8]uril in a 1:2 stoichiometric ratio, formed via non-covalent polymerization driven by strong host-guest cooperation. The nanofiber-like guest is activated to form a supramolecular network polymer with negligible luminescence at 815 nm, showing an ultra-large Stokes shift of up to 240 nm. Interestingly, under oxidant driving, the guest allosterically converts to phenothiazine sulfoxide, which makes the weakly luminescent SOF exhibit strong yellow fluorescence, and the emission blueshifts to 610 nm, with the quantum yield increasing 46-fold to 22.2%. Additionally, the dynamic reversibility of macrocyclic bonding endows the SOFs with reversible and dissociative allosteric properties, enabling thermos-reversible regulation of their luminescence and competitive guest-induced quenching performance. Finally, the allosterically controlled luminescent SOF has been successfully applied to information encryption and logic gates, providing a new perspective for developing intelligent supramolecular materials.