| Summary: | Abstract Artificial aggregation‐induced emission luminogens (AIEgens) have flourished in bio‐applications with the development of synthetic chemistry, which however are plagued by issues like singularity in structures and non‐renewability. The unique structures and renewability of biomass moieties can compensate for these drawbacks, but their properties are hard to design and regulate due to their confined structures. Therefore, it appears to be a reasonable approach to derive AIEgens from abundant biomass (BioAIEgens), integrating the bilateral advantages of both synthetic and natural AIEgens. In this work, the blue‐violet emissive coumarin with its lactone structure serving as a rare natural acceptor, is utilized to construct donor‐π‐acceptor typed BioAIE isomers incorporating the propeller‐like and electron‐donating triphenylamine (TPA) unit. The results show that Cm‐p‐TPA undergoes charge transfer with its keto form, emitting red light at 600 nm, which can be applied to monitor Cu2+ concentration during mitophagy using fluorescence lifetime imaging microscopy because of the excellent biocompatibility, photostability, and specific recognition to Cu2+. This work not only demonstrates the feasibility of utilizing positional isomerization to modulate excited‐state evolutions and resultant optical properties, but also provides evidence for the rationality of constructing biologically‐active BioAIEgens via a biomass‐derivatization concept.
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