Electron‐Deficient Organic Molecules Based on B←N Unit: A N‐Type Room‐Temperature Chemiresistive Sensors with Moisture Resistance

Abstract Organic molecules with tailorable chemical structures, high stability, and solution processability have great potential in the sensing field. Compared with p‐type organic small molecules (OSMs), the electron‐dominated n‐type analogs show superior conductivity when exposed to reducing gases, which can achieve outstanding sensor signal‐to‐noise ratios. However, inadequate humidity resistance at room temperature hinders the development of such molecules. Herein, an A‐D‐π‐D‐A molecular design strategy is proposed based on electron‐deficient B←N units, which results in effective intramolecular charge transport and sensitive responses by extending the π‐conjugation bridge. As a result, the ST‐2BP with A‐D‐π‐D‐A configuration shows a prominent sensitivity of 787 (R _a /R _g ) in 20 ppm NH ₃ at room temperature and an almost initial and stable response under different relative humidity conditions, which is the highest among currently reported OSM sensors. Supported by theoretical calculations and in situ FTIR spectra, it is revealed that B←N units, which function as the active centers mediate the specific ammonia adsorption. This study provides a new understanding of the design of high‐performance room temperature gas sensing materials by decorating B←N units.