Strong dual emission in covalent organic frameworks induced by ESIPT

• Published in: Chemical science (Cambridge) 2019-12, Vol.1 (48), p.1113-1119
• Main Authors: Yin, Hua-Qing, Yin, Fangfei, Yin, Xue-Bo
• Format: Article
• Language: English
• Subjects: Chemical bonds; Chemistry; Emission; Hydrogen bonds; Hydroxyl groups; Interlayers; Moisture content; Solvents
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c9sc03040a

Here we reveal the effects of hydrogen bonds and alkyl groups on the structure and emission of covalent organic frameworks (COFs). Hydrogen bonds improve molecular rigidity leading to high crystallinity and restrict intramolecular rotation to enhance the emission of COFs. An excited-state intramolecular proton transfer (ESIPT) effect for dual emission is achieved via the intramolecular hydrogen bonds between hydroxyl groups and imine bonds. Alkyl groups increase interlayer spacing as a natural "scaffold" and achieve a staggered AB stacking mode to decrease aggregation-caused quenching. Based on the above guidance, COF-4-OH with strong emission is prepared with 2,4,6-triformylphloroglucinol (TFP) and 9,9-dibutyl-2,7-diaminofluorene (DDAF). Strong dual emission is observed and used to differentiate organic solvents with different polarities, to determine the water content in organic solvents, and to detect different pH levels. Our work serves as a guide for the rational design of functional monomers for the preparation of emissive COFs. The introduction of hydroxyl groups and n -butyl groups into COF-4-OH for the construction of COFs with strong dual emission was demonstrated.