Hierarchical Assembly of Fluorinated BODIPY-Based Nanoribbons for Highly Efficient Metal-Free Photocatalytic Hydrogen Production

Self-assembly provides the structural basis for natural photosynthesis, coordinating light-harvesting, energy transfer, and catalysis. However, achieving precise control over assemblies in artificial systems to realize efficient and stable metal-free photocatalysis remains a formidable challenge. Herein, we report the first biomimetic system inspired by the chlorosome, constructed via one-step hierarchical self-assembly of a fluorinated BODIPY amphiphile into well-defined nanoribbons. The integration of perfluoroalkyl chains drives tight molecular packing through fluorous interactions, which crucially enhances the light-harvesting array effect and structural stability. This system achieves exceptional metal-free photocatalytic hydrogen evolution with a rate of 162.5 μmol·g⁻¹·h⁻¹─10 and 30 times higher than that of its nonfluorinated analog PBAH nanoribbons and the molecular control PB, respectively. Under optimized conditions, the system delivers a photocatalytic hydrogen production rate of 1150 μmol·g⁻¹·h⁻¹ with a quantum yield of 0.42% at 550 nm. Mechanistic studies reveal an array-enhanced mechanism in which fluorine-induced close packing promotes exciton delocalization and charge separation, stabilizes a key pyridinyl radical intermediate (>5 ns), collectively establishing a new paradigm for efficient metal-free artificial photosynthesis.