Organic semiconductors offer potential in photovoltaics, photocatalysis, and spintronics but face performance limitations due to rapid charge recombination. In this talk, I will report on the stabilization of separated radical ion pairs in dicyanoperylene bisimide-based helical single molecular stacks, engineered using chiral oligopeptide-polymer chain substituents. We investigated the photophysical properties of these supramolecular organic semiconductor nanowires and the key design factors enabling the unusual charge presence, through experimental, computational, and theoretical approaches. We showed that the anionic radical dicyanoperylene bisimides in these nanowires arise from both thermal and photo-induced self-doping. These processes is facilitated by the nanowires' flexibility, which allows a necessary structural reorganization to reach a stabilized spin decorrelated charge-separated state associated with a distinct equilibrium geometry. Consequently, the assemblies sustain a thermodynamically stable population of radical anions. Moreover, an exceptionally long-lived excess population of these charge carriers can also be photogenerated. The findings demonstrate that balanced structural rigidity in donor-acceptor systems can effectively enable charge separation and significantly extends the usable lifespan of the generated radicals, thus opening avenues for designing more effective materials and devices based on the decoupling of charge separation
efficiency from immediate radical reactivity.