A 2D imine-linked COF with a hitherto unreported htb type topology was synthesized from a linear diamine linker and a judiciously designed tetra-aldehyde building block. This work opens the door to the development of COFs with unprecedented topologies and may broaden the scope of COF functional materials by pore size and pore surface engineering.

We report the design and synthesis of an imine-based two-dimensional covalent organic framework (2D COF) with a novel brick-wall topology by judiciously choosing a tritopic T-shaped building block and a ditopic linear linker. Unlike the main body of COF frameworks reported to-date, which consists of higher-symmetry 2D topologies, the unconventional layered brick-wall topology have only been proposed but never been realized experimentally. The brick-wall structure was characterized by powder X-ray diffraction analysis, FT-IR, solid state ¹³C NMR spectroscopy, nitrogen, and carbon oxide adsorption-desorption measurements as well as theoretical simulations. Our present work opens the door to the design of novel 2D COFs and will broaden the scope of emerging COF materials.

Two stable crystalline hydrazone-linked covalent organic frameworks (COFs) (Bth-Dha and Bth-Dma) containing functional O,N,O'-chelating sites have been designed and successfully synthesized by the Schiff-base condensation reactions between benzene-1,3,5-tricarbohydrazide (Bth) and 2,5-dihydroxyterephthalaldehyde (Dha) or 2,5-dimethoxyterephthal-aldehyde (Dma), respectively. Bth-Dma exhibits strong fluorescence in the solid state and in an aqueous dispersion, while no fluorescence can be observed for Bth-Dha. Interestingly, the as-synthesized Bth-Dma can be used as a turn-off fluorescence sensor for the Fe(III) ion in aqueous solution with outstanding selectivity and sensitivity. The recognition process can be attributed to the coordination interaction between Fe(III) ion and the O,N,O'-chelating sites in the pore wall of Bth-Dma COF, as verified by X-ray photoelectron spectroscopy and ¹H NMR spectroscopy. To the best of our knowledge, this is the first report on the rational design of luminescent COF with predesigned O,N,O'-chelating sites as a fluorescence sensor for highly selective and sensitive metal ion detection. This work may pave the way for designing luminescent COF sensors with functional binding sites for detecting specific metal ions.