Piezofluorochromism in Hierarchical Porous π‐stacked Supermolecular Spring Frameworks from Aromatic Chiral Cages

Abstract Piezochromic materials that exhibit pressure‐dependent luminescence variations are attracting interest with wide potential applications in mechanical sensors, anticounterfeiting and storage devices. Crystalline porous materials (CPMs) have been widely studied in piezochromism for highly tunable luminescence. Nevertheless, reversible and high‐contrast emission response with a wide pressure range is still challenging. Herein, the first example of hierarchical porous cage‐based πOF ( Cage ‐ πOF ‐ 1 ) with spring structure was synthesized by using aromatic chiral cages as building blocks. Its elastic properties evaluated based on the bulk modulus (9.5 GPa) is softer than most reported CPMs and the collapse point (20.0 GPa) significantly exceeds ever reported CPMs. As smart materials, Cage ‐ πOF ‐ 1 displays linear pressure‐dependent emission and achieves a high‐contrast emission difference up to 154 nm. Pressure‐responsive limit is up to 16 GPa, outperforming the CPMs reported so far. Dedicated experiments and density functional theory (DFT) calculations illustrate that π–π interactions‐dominated controllable structural shrinkage and porous‐spring‐structure‐mediated elasticity is responsible for the outstanding piezofluorochromism.