Fluorescence-Enhanced Covalent Organic Frameworks via Integration of Structural Locking with Electron Modulation for...

Highly emissive two-dimensional imine-linked covalent organic frameworks (COFs) remain challenging to construct, as strong interlayer π-π stacking and intramolecular rotation typically induce severe nonradiative decay and fluorescence quenching. Herein, three isostructural pyrene-based COFs had been synthesized, and the hydroxy-functionalized one (OH-COF) exhibited the strongest solid-state photoluminescence with a PLQY of 12.15%. The results revealed that the superior fluorescence of OH-COF originated from the synergistic effects of electronic modulation by the hydroxyl groups and structural locking via hydrogen bonding with imine moieties, which effectively suppress nonradiative transitions from the imine nitrogen lone pairs and thereby enhance the emission. Furthermore, OH-COF, equipped with distinctive dual N,O chelation binding sites, not only delivered outstanding selectivity for metal ions but also enabled a low detection limit of 0.14 μM for Fe³⁺ and a fast response time. This work provides valuable insights for the design of emissive imine COFs, offering a promising strategy for the development of high-performance luminescent sensors.