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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.
Yao et al. (Thu,) studied this question.