Monochromatic Responsive HOF Heterostructures via VIA‐Group‐Based Framework Hybridization for Fully‐Covert Photonic Barcode

Abstract Luminescent responsive heterostructures with region‐domained emission and integrated responsiveness exhibit great potential in information security, but always suffer from the direct exposure of fingerprint information at the initial state, making it easy to decode the hidden confidential information. Herein, the first monochromatic responsive hydrogen‐bonded organic framework (HOF) heterostructures are reported based on VIA‐group‐based framework hybridization toward fully‐covert photonic barcodes. Designed HOF blocks with different VIA‐group elements are integrated via a configuration‐assimilation‐based assembly method to generate the intrinsic monochromatic HOF heterostructures. Differentiated electronegativity of VIA‐group elements endows each HOF block with distinct bonding stability, which triggers different responsive actions to the same stimuli, finally forming the multicolor emission mode at a responsive state. These monochromatic responsive HOF heterostructures can effectively hide the intrinsic fingerprint information, which further demonstrates the fully‐covert photonic coding capability as high‐security anti‐counterfeiting labels. These findings offer novel insight on the exploitation of smart‐responsive hetero‐HOF systems for advanced information encryption and anticounterfeiting applications.