Novel core–shell materials SiO2@Tb-MOF for the incorporation of spiropyran molecules and its application in dynamic advanced information encryption

Abstract

Dynamic fluorescent switches with multiple light outputs offer promising opportunities for advanced security encryption. However, the achievement of dynamic emission, particularly when based on the timing of external stimuli, continues to present a significant challenge. Herein, a unique dynamic fluorescent switch was developed by integrating spiropyran molecules (SP) into a core–shell structure (SiO₂@Tb-MOF). The core–shell structure, derived from lanthanide complexes and silica microspheres, was synthesized under solvothermal conditions. This structure not only preserves the green fluorescence emission of Tb-MOF, but also results in a substantial specific surface area and mesoporous pore size from SiO₂, which is advantageous for incorporating SP molecules to create a dynamic fluorescent switch, SP ⊂ SiO₂@Tb-MOF. Upon exposure to ultraviolet light, SP gradually transitions into the merocyanine form (MC), displaying a pronounced absorption band at approximately 550 nm. Concurrently, a fluorescence resonance energy transfer (FRET) process is initiated between Tb³⁺ and the merocyanine isomers. With prolonged exposure to UV light, the fluorescence color shifts progressively from green to red, facilitated by the ongoing FRET process. Moreover, SP ⊂ SiO₂@Tb-MOF is doped with polydimethylsiloxane to fabricate a film. Utilizing time-dependent fluorescence, dynamic encryption patterns and advanced information encryption were investigated. This work provides a design basis for how to better construct core–shell structures and combine them with SP molecules to prepare dynamic fluorescent materials, and paves a way for constructing advanced encryption materials with higher safety requirements.