Exciton Regulation and Fluorescence Switching via Redox‐Responsive Heterojunction Interfaces

Abstract Redox‐responsive fluorescence regulation at heterointerfaces remains a critically underdeveloped yet strategically significant domain in advanced chemical sensing. Herein, we present an exciton modulation strategy enabled by heterojunction engineering between electron‐rich CdSe quantum dots and an electron‐deficient covalent triazine framework (CTF). This type‐I CdSe@CTF heterostructure achieves nanoscale electronic decoupling and directional charge redistribution, unveiling a previously unreported fluorescence‐switching mechanism governed by redox‐triggered interfacial reconfiguration. Beyond excitonic regulation, the heterostructure intrinsically mimics oxidase‐like catalysis, enabling dual fluorescence–colorimetric readouts within a unified excitonic framework. When embedded into flexible electrospun membranes and combined with artificial neural network (ANN)‐based image recognition, the system offers adaptive and intelligent detection under bio‐relevant conditions. This study establishes a molecularly encoded design paradigm that bridges exciton dynamics, redox chemistry, and wearable photonic sensing, offering a blueprint for the development of multifunctional bioelectronic platforms.