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Here, we report the rational molecular engineering of wafer\u2010scale, ultrathin 2D imine\u2010linked COF films via interfacial polymerization, illustrating precise control over electronic band structure, nanoscale porosity, and hygroscopicity for exceptional humidity sensing, thus unveiling the underlying structural\u2010property correlations. By simultaneously incorporating triazine and multi\u2010hydroxyl groups, the humidity sensor based on 2D COF\n                    <jats:sub>TPT\u2010THTA<\/jats:sub>\n                    exhibits a high sensitivity (66\u00a0124% per %RH), fast response\/recovery times (0.12\/0.40 s), and minimal hysteresis (\u0394RH \u2248 1.0%), due to a synergistic effect of high structural polarity, excellent hydrophilicity, and the nanoscale confined crystalline pore framework. The nanometer\u2010scale thickness and ultrasmooth surface facilitate efficient charge transport and water adsorption kinetics. Leveraging these properties, we further demonstrate a prototypical wearable sensor for real\u2010time respiratory monitoring, which is capable of accurately tracking physiological states and detecting pathological patterns (asthma, apnea). This work establishes a fundamental molecular engineering paradigm for 2D COF film\u2010based sensors, bridging the gap between programmable materials and next\u2010generation high\u2010performance health diagnostics.\n                  <\/jats:p>","DOI":"10.1002\/adma.202517182","type":"journal-article","created":{"date-parts":[[2026,3,8]],"date-time":"2026-03-08T21:27:12Z","timestamp":1773005232000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Wafer\u2010Scale Synthesis of Molecularly Engineered 2D Covalent Organic Framework Films for Highly\u2010Sensitive and Rapid\u2010Response Humidity Sensing"],"prefix":"10.1002","volume":"38","author":[{"given":"Liangyu","family":"Dong","sequence":"first","affiliation":[{"name":"State Key Laboratory of Supramolecular Structure and Materials Jilin University Changchun 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