Hydro-Photo-Thermo-Responsive Multicolor Luminescence Switching of a Ternary MOF Hybrid for Advanced Information Anticounterfeiting

Small. 2023 Dec 14:e2305624. doi: 10.1002/smll.202305624. Online ahead of print.

Abstract

Developing smart materials capable of solid-state multicolor photoluminescence (PL) switching in response to multistimuli is highly desirable for advanced anticounterfeiting. Here, a ternary MOF hybrid showing hydro-photo-thermo-responsive multicolor PL switching in the solid state is presented. This hybrid is constructed by co-immobilizing Eu3+ and methyl viologen (MV) cations within an anionic MOF via the cation-exchange approach. The confined guest cations are well arranged in the framework channels, facilitating the synergistic realization of stimuli-responsive multiple PL color-switching through intermolecular coupling. The hybrid undergoes a rapid and reversible PL color-switching from red to blue upon water simulation, which is achieved by activating the blue emission of the framework linker while simultaneously quenching the Eu3+ emission. Furthermore, the hybrid displays photo-thermo-responsive PL switching from red to dark. UV-light irradiation or heating triggers the chromic conversion of MV to its colored radical form, which exhibits perfect spectral overlap with Eu3+ , thus activating Förster resonance energy transfer (FRET) from Eu3+ to MV radicals and quenching the Eu3+ emission. Inspired by these results, PL morse patterns are designed and fabricated using a novel triple-level encryption strategy, showcasing the exciting potential of this hybrid in advanced anticounterfeiting applications.

Keywords: MOF hybrids; anticounterfeiting; lanthanide luminescence; multicolor luminescence switching; multistimuli-responsive materials.