A hydrogen-bonded organic framework containing fluorescent carbazole and responsive pyridyl units for sensing organic acids

Abstract

Hydrogen-bonded organic frameworks (HOFs) are a promising candidate for optical sensing, but the lack of effective design strategies poses significant challenges to the construction of HOFs for organic acid sensing. In this work, the first HOF for organic acid sensing is reported by constructing a multiple-pyridine carbazole-based dense HOF, namely HOF-FJU-206, from a tripyridine-carbazole molecular 3,6-bis(pyridin-4-yl)-9-(4-(pyridin-4-yl)phenyl)-9H-carbazole (CPPY) with carbazole center for luminescence, pyridyl sites for its responsive of hydrogen proton, and narrow channels in the dense framework for the diffusion of hydrogen protons. HOF-FJU-206 exhibits differential responsively fluorescence sensing and recovery properties to formic, acetic, and propionic acids with different molecular sizes and pKa value (acid dissociation constant). The dissociation degree of various acids can be determined by analyzing the slope of changes in both peak wavelength and intensity of in-situ fluorescence, which easily enables the dual-corrective recognition of different acids. The varying degree of protonation at pyridine sites is proved to be the reason for differential sensing of various acids, as demonstrated by 1H NMR spectra, X-ray photoelectron spectroscopy (XPS) characterization, and modeling studies.