Achieving Stable and Switchable Ultralong Room-Temperature Phosphorescence from Polymer-Based Luminescent Materials with Three-Dimensional Covalent Networks for Light-Manipulated Anticounterfeiting.

Developing polymer-based organic afterglow materials with switchable ultralong organic phosphorescence (UOP) that are insensitive to moisture remains challenging. Herein, two organic luminogens, BBCC and BBCS, were synthesized by attaching 7-benzo[]carbazole (BBC) to benzophenone and diphenyl sulfone. These two emitters were employed as guest molecules and doped into epoxy polymers (EPs), which were constructed by in situ polymerization to achieve polymer materials BBCC-EP and BBCS-EP. It was found that BBCC-EP and BBCS-EP films exhibited significant photoactivated UOP properties. After light irradiation, they could produce a conspicuous organic afterglow with phosphorescence quantum yields and lifetimes up to 5.35% and 1.91 s, respectively. Meanwhile, BBCS-EP also presented photochromic characteristics. Upon thermal annealing, the UOP could be turned off, and the polymer films recovered to their pristine state, showing switchable organic afterglow. In addition, BBCC-EP and BBCS-EP displayed excellent water resistance and still produced obvious UOP after soaking in water for 4 weeks. Inspired by the unique photoactivated UOP and photochromic properties, BBCC and BBCS in the mixtures of diglycidyl ether of bisphenol A (DGEBA) and 1,3-propanediamine were employed as security inks for light-controlled multilevel anticounterfeiting. This work may provide helpful guidance for developing photostimuli-responsive polymer-based organic afterglow materials, especially those with stable UOP under ambient conditions.