Sulfone-functionalized stereoisomeric [3]radialene displays guest induced modulation of porous frameworks and critical crystallization-induced near-infrared emission

-cyclic radialene ring. The stability of these structures is further enhanced by sulfone-embedded aromatics and guest solvent molecules, establishing a network of multivalent molecular interactions. Remarkably, TTRO-based materials exhibit crystallization-induced emission in the near-infrared (NIR) region (650-1000 nm), transitioning from non-emissive amorphous powders to exhibiting strong photoluminescence (up to 24.1%) in guest-involved porous crystalline frameworks. Time-resolved fluorescence and computational analyses reveal that the dynamic stacking geometry of TTRO units, combined with multivalent sulfone-based intermolecular interactions with guest molecules, modulates the reorganization energy within the frameworks, thereby tuning solid-state emission. These findings provide new insights and strategies for designing NIR luminophores through crystalline engineering of [3]radialene materials.