Porous Organic Frameworks Constructed by the Synergetic Effect of Covalent Bonds and Hydrogen Bonds for the Selective Identification and Detection of Explosives.

Abstract

Covalent organic frameworks (COFs) and hydrogen-bonded organic frameworks (HOFs) have emerged as novel platforms for material design and functional explorations. Here, we report an unconventional structural organic framework (named CHOF-1) combined with 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 5-hydroxyisophthalaldehyde (HP) through the synergetic effect of covalent bonds and hydrogen bonds. CHOF-1 contains two different pores and is an eclipsed AA-stacking model with high thermal stability. It exhibits selective "turn-off" and red shift fluorescence responses toward 4-nitrophenol (4-NP) and 2,4,6-trinitrophenol (TNP) in ethanol, respectively, and the low detection limit was 8.78 μM for 4-NP and 11.1 μM for TNP. It has satisfactory recovery in the detection of 4-NP and TNP in practical water samples. The fluorescence quenching of CHOF-1 caused by 4-NP is attributed to the absorption competition quenching (ACQ) mechanism. In the structure of CHOF-1, the hydroxyl of TNP has strong acidity and can form strong hydrogen bonds with the unreacted NH2. Then, the crystalline structure of CHOF-1 decomposed and the electron structure of the photophore changed; thus, the fluorescence spectra red-shifted. This is a novel example of a covalent bond and hydrogen bonds combined organic framework (CHOF). This work not only demonstrates a synthesis strategy of the first novel structural organic framework through the synergetic effect of covalent bonds and hydrogen bonds but also provides a fluorescent sensing material for the detection of explosives 4-NP and TNP with high selectivity and sensitivity.