Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application.
High crystallinity of covalent organic frameworks (COFs) with dual fluorescence emissions has not been reported so far. Here, we show the rational design and preparation of high-crystallinity COF TzDa via the synergetic interaction of docking sites and hydrogen bonds: 4,4',4″-(1,3,5-Triazine-2,4,6-triyl)trianiline (Tz) with the docking site and 2,5-dihydroxyterephthalaldehyde (Da) with the OH group are employed to synthesize the imine-linked two-dimensional high-crystallinity layered structure TzDa. The prepared mesoporous TzDa (ca. 36 Å) exhibits high thermal and chemical stability. The intramolecular charge transfer (ICT) and excited-state intramolecular proton transfer (ESIPT) effects bring TzDa two main fluorescence emissions around 500 and 590 nm. Water molecules can interfere with the ICT and ESIPT effects, allowing the development of a ratiometric fluorescent sensor for water in organic solvents. The proposed sensor shows high sensitivity to trace water in conventional organic solvents. The high stability of TzDa allows its recyclable uses for trace water detection. This work not only offers a platform for the construction of high-crystallinity COFs, but also provides a rational design of COFs with dual fluorescence emissions for ratiometric sensing applications.
Design of stable adsorbents for selective gold recovery with large capacity and fast adsorption kinetics is of great challenge, but significant for the economy and the environment. Herein, we show the design and preparation of an irreversible amide‐linked covalent organic framework (COF) JNU‐1 via a building block exchange strategy for efficient recovery of gold. JNU‐1 was synthesized through the exchange of 4,4′‐biphenyldicarboxaldehyde (BA) in mother COF TzBA consisting of 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline (Tz) and BA with terephthaloyl chloride. The irreversible amide linked JNU‐1 gave good stability, unprecedented fast kinetics, excellent selectivity and outstanding adsorption capacity for gold recovery. X‐ray photoelectron spectroscopy along with thermodynamic study and quantum mechanics calculation reveals that the excellent performance of JNU‐1 for gold recovery results from the formation of hydrogen bonds C(N)−H⋅⋅⋅Cl and coordinate interaction of O and Au. The rational design of irreversible bonds as both inherent linkage and functional groups in COFs is a promising way to prepare stable COFs for diverse applications.
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