A Phototautomeric3D Covalent Organic Framework forRatiometric Fluorescence Humidity Sensing

Photoinduced proton transfer is an essential photochemical process for designing photocatalysts, white light emitters, bioimaging, and fluorescence sensing materials. However, deliberate control of the excited/ground states and meticulous manipulation of the excited state intramolecular proton transfer (ESIPT) pathway constitute a significant challenge in liquids and dense solids. Here, we present the integration of a hydronaphthoquinone fluorophore into a crystalline, porous, phototautomeric dynamic 3D covalent organic framework (COF) to show guest-induced fluorescence turn-on, emission redshift enhancement, and shortened lifetimes for ratiometric fluorescence humidity sensing. Theoretical and spectroscopic studies provide mechanistic insights into the conformational dynamics, charge transfer coupled with local excitation, and ground-state uphill regulation for the multiple tautomers. We illustrate the sensitive, rapid, steady, and self-calibrated ratiometric fluorescence sensing for a wide range of humidity benefiting from the architectural and chemical robustness and crystallinity of such a phototautomeric 3D COF. These findings provide molecular insights into the design of functional porous materials that integrate host–guest mutual recognition and photoelectronic response for multiplex molecular sensing for environmental monitoring and biomedical diagnostics applications.