Highly photoelectrical responsive and controllable supramolecular helical assemblies with dual functionalities as photo-organocatalysts

Despite the enhanced photocatalytic efficiency of H-type assemblies with long-range ordered cofacial π -stacking (stemming from improved carrier mobility and stability), current studies predominantly concentrate on monomeric organic photocatalysts in organic media. We develop hierarchically ordered dipeptide-perylene diimide assemblies that synergistically integrate photocatalytic and organic catalytic functions, mimicking nature photosynthesis system. Through systematic modulation of solvent composition , pH, and fabrication protocols, precisely tunable nanoarchitectures spanning nanofibers , twisted nanorods , "donut" assemblies, and spherical nanostructures were constructed from lamellar building units in aqueous media. Architecture-dependent photoelectrical responsivity achieved a maximum of 2.0 μA cm −2 , representing a 5.8-fold enhancement. Highly ordered assemblies exhibited exceptional triethylamine sensing performance (97.8 μA cm −2 , 65-fold amplification) with a 4.7-fold lower detection limit than disordered aggregates. Remarkably, this system established dual-functional photo-organocatalytic activity, attaining 91.7 % conversion efficiency in tandem photooxidation/alkylation of 2-arylindoles. • Kinetical control of assembly pathway to generate precisely tunable nanostructure. • Hierarchical assemblies enable 5.8 × optoelectronic tuning & 65 × TEA sensing. • Green tandem photooxidation/alkylation achieves 91.7 % yield (H₂O/visible light/O 2 /rt). • Long-range ordering and photo-organocatalytic spacing optimize catalytic efficiency.