Far-red-excitable ultra-long-lived organic photocatalyst for photocatalytic decaging

Photomodulation technology, characterized by its high spatiotemporal resolution, has emerged as a transformative approach for precise, rapid, and non-invasive regulation of intricate cellular signaling networks, offering unprecedented opportunities for biomedical research. Nevertheless, the in vivo implementation of wireless photomodulation remains constrained by the inherent limitations of conventional photoresponsive systems. Addressing this challenge, we report a BODIPY-based photocatalyst with exceptional red-light responsiveness (λ > 630 nm). Transient spectroscopic studies show that this photocatalyst exhibits the feature with solvent polarity-switching excited state dynamics. In addition, we observed ultralong triplet-state lifetimes (590 μs in tetrahydrofuran; 862 μs in toluene), which is favorable for establishing a far-red-light-driven photocatalytic decaging platform that synergistically integrates the BODIPY photocatalyst with endogenous NADH as the intrinsic electron donor. Crucially, this system demonstrates robust in vivo efficacy, achieving significant tumor growth suppression in murine tumor models through localized prodrug activation. This work not only provides fundamental insights into engineering long-lived triplet states in metal-free organic photocatalysts but also pioneers a biocompatible strategy for spatiotemporally controlled therapeutic interventions, bridging the gap between advanced photochemistry and precision biomedicine.