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This study presents a novel boron‐difluoride complex‐based fluorescent nanofilm sensor capable of detecting sarin vapors in the environment by reporting an output fluorescence signal. The sensor's evaluation demonstrated an exceptionally low detection limit for sarin vapor, even in the presence of various interfering gases, with theoretical and practical limits of detection of 0.7 and 1 ppb, respectively. The sensor featured a rapid response time (less than 2 s), a broad linear detection range (1 ppb–1000 ppm), and superior selectivity for sarin vapor over a group of interfering analytes, outperforming existing sarin sensors. Mechanistic study indicates that the sensor's heightened sensitivity to sarin vapor is due to the robust affinity of nitrogen atoms within the core BODIQ unit for sarin. Additionally, the tetraphenylethylene structure with steric hindrance effectively inhibits the tight packing of BODIQ derivatives, and forms numerous microporous structures in the self‐assembled nanofilm, which are beneficial for the mass transfer, enhancing the sensor efficiency in detecting vapors. Furthermore, we have achieved the differentiation of sarin, diethyl chlorophosphate, and HCl vapor through the analysis of sensing kinetic. This fluorescent sensor opens new avenues for sustainable, low‐cost, and environment‐friendly portable devices, as well as for environmental monitoring and tracking applications. [ABSTRACT FROM AUTHOR]

A novel fluorescent nanofilm DBAP-ETTA has been developed for diethyl chlorophosphate (DCP) vapor detection with high sensitivity and selectivity. Its smooth, homogeneous structure and large Stokes shift enable significant fluorescence quenching upon DCP exposure. The protonation-based sensing mechanism makes it ideal for real-time, portable DCP vapor sensing. [ABSTRACT FROM AUTHOR]