Novel Stimuli-Responsive Spiropyran-Based Switch@HOFs Materials Enable Dynamic Anticounterfeiting

Abstract

Developing smart fluorescent materials having very advanced levels, showing dynamic displays of encrypted messaging, remains a huge challenge. In this paper, we present a unique method based on combining a common photochromic molecule spiropyran (SP) with hydrogen-bonded organic frameworks (HOFs), which allows for reversible switching of SP in solid states and shows dynamic displays of encrypted information. With the irradiation time extended, the fluorescence emission undergo an evident transformation from yellow-green to orange to red, because of the fluorescence resonance energy transfer (FRET) process between the unique HOFs and merocyanine (MC) isomer. By doping with polydimethylsiloxane (PDMS), we obtained free-standing membranes with high flexibility and mechanical strength, which can be reversibly and repeatedly bent and folded at angles of >90°. Notably, the comparison of fatigue resistance between SP2/PDMS (can be used for no more than 5 times) and SP2 ⊂ HOF2/PDMS (can be used for more than 100 times) further proved the importance of HOFs. This composite system has many advantages: (1) it has diverse dynamic fluorescence emission and visible colors regulated by ultraviolet radiation with high contrast and can be reversibly converted; (2) these changes in behavior can be achieved by simple UV illumination; and (3) compared with previous work, this work not only shows the dynamic fluorescence emission, but also shows the dynamic information during the decryption.