A molecular roadmap towards organic donor-acceptor complexes with high-performance thermoelectric response

Abstract As a unique class of molecular electronic materials, organic donor–acceptor complexes now exhibit tantalizing prospect for heat–electricity interconversion. Over the past decades, in design these materials thermoelectric applications, consistent efforts have been made to synthesize wide variety structures and characterize their properties. However, hitherto, one paramount conundrums, namely lack systematic principles, has not addressed yet. Here, based on ab initio calculations, by comprehensively examining underlying correlation among power factors, non-intuitive transport processes, fundamental chemical 13 prototypical complexes, we establish unified roadmap rational development with increased response. We corroborate that energy levels frontier orbitals isolated donor acceptor molecules control charge transfer, property, transport, performance solid-state complexes. Our results demonstrate tailoring suitable energy-level difference between donor’s highest occupied orbital acceptor’s lowest unoccupied holds key achieving an outstanding factor. Moreover, reveal charge-transfer-caused Coulomb scattering governs