Fast and Selective Luminescent Sensing by Langmuir–Schaeffer Films Based on Controlled Assembly of Perylene Bisimide Modified with A Cyclometalated AuIII Complex

Abstract Condensed films of functional luminophores dominated by the magnitude and dimensionality of the intermolecular interactions play important roles in sensing performance. However, controlling the molecular assembly and regulating photophysical properties remain challenging. In this study, a new luminophore, ortho ‐PBI‐Au, was synthesized by anchoring a cyclometalated alkynyl‐gold(III) unit at the ortho ‐position of perylene bisimide. An unprecedented T‐type packing model driven by weak Au‐π interaction and Au−H bonds was observed, laying foundation for striking properties of the luminophore. Controlled assembly of ortho ‐PBI‐Au at the air‐water interface, realized using the classical Langmuir–Schaeffer technique, afforded the obtained luminescent films with different packing structures. With an optimized film, sensitive, selective, and rapid detection of a hazardous new psychoactive substance, phenylethylamine (PEA), was achieved. The detection limit, response time, and recovery time were <4 ppb, <1 s, and <5 s, respectively, surpassing the performance of the PEA sensors known thus far. The relationship between the characters of films and the sensing performance was systematically examined by grey relational analysis (GRA). The present study suggests that designing novel molecular aggregation with definite adlayer structure is a crucial strategy to enhance the sensing performance, which could be favorable for the film‐based fluorescent sensors.