Boosting Multicolor Emission Enhancement in Two-Dimensional Covalent–Organic Frameworks via the Pressure-Tuned π–π Stacking Mode

Covalent–organic frameworks (COFs) are dynamic covalent porous organic materials constructed from emissive molecular organic building blocks. However, most two-dimensional (2D) COFs are nonemissive or weakly emissive in the solid state owing to the intramolecular rotation and vibration together with strong π–π interactions. Herein, we report a pressure strategy to achieve the bright multicolor emission from yellow to red in the 2D triazine triphenyl imine COF (TTI-COF). Intriguingly, the TTI-COF experiences a 24-fold enhancement under a mild pressure of 2.7 GPa compared with the initial state. Joint experimental and theoretical results reveal that the restricted intramolecular chemical bond vibrations and the reduced π–π interactions originating from the offset stacking mode account for the significant pressure-induced emission enhancement. Furthermore, such piezochromic behavior may be ascribed to the decreased energy gap and enhanced intermolecular interaction. Our investigation offers constructive guidelines for designing 2D COF materials with high photoluminescence performance.