Cooperative supramolecular polymers with anthracene‒endoperoxide photo-switching for fluorescent anti-counterfeiting

Abstract

Innovative technologies are highly pursued for the detection and avoidance of counterfeiting in modern information society. Herein, we report the construction of photo-responsive supramolecular polymers toward fluorescent anti-counterfeit applications, by taking advantage of multicycle anthracene‒endoperoxide switching properties. Due to σ-metalation effect, photo-oxygenation of anthracene to endoperoxide is proceeded under the mild visible light irradiation conditions, while the backward conversion occurs spontaneously at room temperature. Supramolecular polymers are formed with cooperative nucleation‒elongation mechanism, which facilitate fluorescence resonance energy transfer process via two-component co-assembly strategy. Fluorescence resonance energy transfer efficiency is delicately regulated by either light-triggered anthracene‒endoperoxide conversion or vapor-induced monomer–polymer transition, leading to high-contrast fluorescent changes among three different states. On this basis, dual-mode anti-counterfeiting patterns have been successfully fabricated via inkjet printing techniques. Hence, cooperative supramolecular polymerization of photo-fluorochromic molecules represents an efficient approach toward high-performance anti-counterfeit materials with enhanced security reliability, fast response, and ease of operation.