Mechanical tough and multicolor aggregation-induced emissive polymeric hydrogels for fluorescent patterning

Abstract

Aggregation-induced emissive fluorogens (AIEgens) are promising building blocks for fluorescent polymeric hydrogels (FPHs) because intense fluorescence intensities are usually guaranteed by spontaneous aggregates of hydrophobic AIEgens in a hydrophilic polymer network. However, most AIE-active FPHs are single-color fluorescent and cannot display tunable emission colors. Additionally, efforts to produce mechanically strong AIE-active hydrogels have been largely ignored, restricting their potential uses. Herein, we present the synthesis of an AIE-active methyl picolinate-substituted 1,8-naphthalimide monomer (MP-NI) for fabricating mechanical tough and multicolor FPHs. Owing to the introduction of bulky and coordinative methyl picolinate group, these specially designed MP-NI molecules were forced to adopt propeller-shaped conformation that renders them with intense aggregation-induced blue emission. Moreover, the MP-NI moieties grafted in a hydrogel matrix can sensitize red and green fluorescence of Eu³⁺and Tb³⁺via antenna effect. Consequently, multicolor fluorescent hydrogels that sustain a high stress of 1 MPa were obtained by chemically introducing MP-NI moieties into dually cross-linked alginate polymer networks with high-density metal (Ca²⁺/Tb³⁺/Eu³⁺) coordination and hydrogen bonding crosslinks. Their capacity to enable the writing of arbitrary multicolor fluorescent patterns using Eu³⁺/Tb³⁺ as inks were finally demonstrated, suggesting their potential uses for smart display and information encryption.