Computational Design of Isomeric Naphthalenediimide–Naphthodithiophene (NDI–NDT) Copolymers for Organic Electronics

This study presents a comprehensive investigation of conjugated donor–acceptor (D–A) copolymers based on naphthalenediimide (NDI) and two structural isomers of naphthodithiophene (NDT), i.e., linear (L-NDT) and angular (A-NDT), designated as NDI–L-NDT and NDI–A-NDT, respectively. By systematically analyzing their molecular structure, (opto)electronic properties, photovoltaic performance, morphological analysis, and mechanical stability, this study reveals the profound influence of donor isomerism on material properties, relevant to organic electronic applications. In particular, NDI–L-NDT exhibits a lower bandgap attributed to its extended donor π-conjugation and nearly coplanar D–A conformation compared to NDI–A-NDT. NDI–A-NDT demonstrates superior photovoltaic performance due to its higher power conversion efficiency compared to its linear counterpart. Morphological studies based on molecular dynamics simulations reveal that films of both copolymers exhibit similar levels of crystallinity. However, NDI–L-NDT possesses greater thermal stability and mechanical flexibility, capable of withstanding up to 100% strain without cracking, attributed to its dynamic conformational adaptability, making it a promising candidate for flexible electronic applications. This work reveals the potential of structural isomerism in fine-tuning D–A copolymers for multifunctional roles, as donors, acceptors, or single-component materials in next-generation organic electronic devices.