Rational Design of Double Cable Organic Semiconducting Polymers and Their Functional Hybrids as Photocatalysts for Artificial Photosynthesis

Abstract

The application of organic semiconducting polymers (OSPs) as photocatalysts for the artificial photosynthesis of solar fuels has attracted significant attention over the past decade. OSPs typically exhibit high exciton binding energies (0.1-1.0 eV), which can hinder charge separation and contribute to rapid charge recombination, thereby limiting the efficiency of light-driven processes. Therefore, effective management of photogenerated excitons is of paramount importance. One of the key strategies for exciton management involves enhancing charge separation by physically interfacing an electron donor (D) material with an electron acceptor (A) possessing a higher electron affinity. This bulk heterojunction (BHJ) arrangement has been widely exploited to interface small molecule and polymeric organic semiconductors with fullerenes and non-fullerene acceptors (NFAs). Building on advances in BHJ architectures, a natural evolution has been the development of single component materials in which the D-A components are covalently linked. Such covalent integration spatially confines the donor and acceptor components, facilitating electronic communication between them while simplifying photoac

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