Chemically stable chromenoquinoline (CQ)-based covalent organic frameworks (COFs) were constructed by postsynthetic conversion of imine COFs. The key step of an intramolecular Povarov reaction can transform a preintegrated alkyne group to bridge the benzene rings on both sides of the imine linkage via chemical bonds, affording a ladder-type CQ linkage. This novel approach achieves a high cyclization degree of 80−90%, which endows the CQ-COFs with excellent chemical stability toward strong acid, base, and redox reagents. The synthetic approach can be applied to various monomers with different symmetries and functional core moieties. The absorption and fluorescence intensities of CQ-COFs are sensitive to acid, which allows for dual-mode sensing of strongly acidic environments.

Covalent organic frameworks have shown considerable application potential and exceptional properties in the construction of stimulus-responsive materials. Here, we designed a sweat-responsive covalent organic framework film for material-based fingerprint liveness detection. When exposed to human sweat, the COFTPDA-TFPy film can transform from yellow to red. The COFTPDA-TFPy film, when touched by living fingers, can produce the naked-eye-identified fingerprint pattern through the sweat-induced color change, while artificial fake fingerprints cannot. This technique, which we named material-based liveness detection, can thus intuitively discern living fingers from fake fingerprints with a 100% accuracy rate. Additionally, the distribution of sweat pores on human skin can also be collected and analyzed by shortening the contact time. By merely washing them with ethanol, all the samples can be utilized again. This work inventively accomplished material-based liveness detection and naked-eye-identified sweat pore analysis and highlighted their potential for use in clinical research and personal identification.

Comprehensive Summary Vinylene linked covalent organic frameworks (COFs) have drawn extensive attention due to their desirable stability, carbon conjugation and opto‐electronic properties. Suitable catalyst is a key factor in the synthesis of vinylene linked COFs, and proton acids and bases are widely reported as catalysts so far. Herein, we report the synthesis of vinylene linked COFs using Lewis acid ZnCl2 as catalyst for the first time. Four COFs with hexagonal pores of different sizes are synthesized by the reaction of 2,4,6‐trimethyl triazine and a series of aromatic aldehydes.