Organic crystalline nanoparticles with a long-lived charge-separated state for efficient photocatalytic hydrogen...

Photocatalysis offers a promising approach for renewable energy conversion and storage, but short lifetimes of charge-separated states in photocatalysts due to charge recombination limit its utility. Here we report an organic molecule with an acceptor-donor-acceptor configuration that can self assemble into highly crystalline nanoparticles. Transient absorption spectroscopy reveals that these crystalline assemblies can induce an ultra-long-lived charge-separated state of up to 1.2 s, attributed to initial symmetry-breaking charge separation, followed by charge hopping across closely packed molecules. These self-assembled nanoparticles have an impressive photocatalytic H₂ evolution rate of 126 mmol g^-1 h^-1 with an external quantum efficiency of 12% at 550 nm under optimized conditions. This system shows a remarkable stability with 220 million turnover numbers (per particle) over the 77 h of operation. These findings suggest that rational design of organic molecules and their aggregates is vital for improving light-induced charge separation and for developing highly efficient, stable and scalable organic photocatalysts.