Abstract

AbstractUltralong organic phosphorescence (UOP) is essential for potential applications in bioelectronics and optoelectronics. However, the precise design of UOP materials remains a formidable challenge. Herein, a facile strategy is presented to confine dimeric chromophores for triggering UOP emission, based on the manipulation of the carbonyl, sulfonyl, and amino groups within organic phosphors. The experimental data reveal that saccharin analogs in crystals containing dimeric chromophores, confined by the (3D) hydrogen‐bonded networks, exhibit ultralong emission lifetime of up to 635 ms under ambient conditions. Whereas for saccharin analogue crystals lacking dimeric chromophores, the lifetime decreases to 54 ms, resulting in the absence of UOP emission. Moreover, the non‐toxic saccharin crystals with UOP have succeeded in drug anti‐counterfeiting. These findings will open a novel avenue for the design UOP materials and broaden the domain of UOP to diverse applications.

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