Modulation of Deep-Red to Near-Infrared Room-Temperature Charge-Transfer Phosphorescence of Crystalline “Pyrene Box” Cages by Coupled Ion/Guest Structural Self-Assembly

Organic cocrystals obtained from multicomponent self-assembly have garnered considerable attention due to their distinct phosphorescence properties and broad applications. Yet, there have been limited reports on cocrystal systems that showcase efficient deep-red to near-infrared (NIR) charge-transfer (CT) phosphorescence. Furthermore, effective strategies to modulate the emission pathways of both fluorescence and phosphorescence remain underexplored. In this work, we dedicated our work to four distinct self-assembled cocrystals called “pyrene box” cages using 1,3,6,8-pyrenetetrasulfonate anions (PTS^4-), 4-iodoaniline (1), guanidinium (G⁺), diaminoguanidinium (A₂G⁺), and hydrated K⁺ countercations. The binding of such cations to PTS^4- platforms adaptively modulates their supramolecular stacking self-assembly with guest molecules 1, allowing to steer the fluorescence and phosphorescence pathways. Notably, the confinement of guest molecule 1 within “pyrene box” PTSK{1} and PTSG{1} cages leads to an efficient deep-red to NIR CT phosphorescence emission. The addition of fuming gases like triethylamine and HCl allows reversible pH modulations of guest binding, which in turn induce a reversible transition of the “pyrene box” cage between fluorescence and phosphorescence states. This capability was further illustrated through a proof-of-concept demonstration in shrimp freshness detection. Our findings not only lay a foundation for future supramolecular designs leveraging weak intermolecular host-guest interactions to engineer excited states in interacting chromophores but also broaden the prospective applications of room-temperature phosphorescence materials in food safety detection.