Smart‐Responsive HOF Heterostructures with Multiple Spatial‐Resolved Emission Modes toward Photonic Security Platform

Luminescent hydrogen‐bonded organic frameworks (HOFs) with the unique dynamics and versatile functional sites hold great potential application in information security, yet most of responsive HOFs focus on the single‐component framework with restrained emission control, limiting further applications in advanced confidential information protection. Herein, the first smart‐responsive HOF heterostructure with multiple spatial‐resolved emission modes for covert photonic security platform is reported. The HOF heterostructures are prepared by integrating different HOFs into a single microwire based on a hydrogen‐bond‐assisted epitaxial growth method. The distinct responsive behaviors of HOFs permit the heterostructure to simultaneously display the thermochromism via the framework transformation and the acidichromism via the protonation effect, thus generating multiple emission modes. The dual stimuli‐controlled spatial‐resolved emission modes constitute the fingerprint of a heterostructure, and enable the establishment of the smart‐responsive photonic barcode with multiple convert states, which further demonstrate the dynamic coding capability and enhanced security in anticounterfeiting label applications. These results offer a promising route to design function‐oriented smart responsive HOF microdevices toward advanced anticounterfeiting applications. The smart‐responsive hydrogen‐bonded organic framework (HOF) heterostructure is first realized based on the differentiated design on high‐electronegative atoms of building blocks, which exhibit dual‐stimuli‐controlled spatial‐resolved emission modes, facilitating the construction of responsive photonic barcodes with multiple convert states. These results provide enlightenment on the function‐oriented design of smart‐responsive HOF heterosystem for advanced anticounterfeiting and information security applications.